Osmania University College of Technology

OSMANIA UNIVERSITY COLLEGE OF
TECHNOLOGY
A SEMINAR ON E1CB ELIMINATION
BY
SRAVAN KUMAR.D
M.PHARMACY 1 ST YR 1ST SEM
PHARMACEUTICAL CHEMISTRY
ROLL NO:1008-10-884-008
E1CB ELIMINATION
 CONTENTS
 INTRODUCTION
 TYPES OF ELIMINATION
 STEREOCHEMISTRY OF
E1CB
 E1,E2,E1CB DIFFERENCES
 APPLICATIONS
 REFERNCES

Alkyl Halides React with
Nucleophiles and Bases
 Alkyl halides are polarized at the carbon-halide bond,
making the carbon electrophilic
 Nucleophiles will replace the halide in C-X bonds of
many alkyl halides(reaction as Lewis base)
 Nucleophiles that are Brønsted bases produce
elimination
2
11.7 Elimination Reactions of
Alkyl Halides: Zaitsev’s Rule
 Elimination is an alternative pathway to substitution
 Opposite of addition
 Generates an alkene
 Can compete with substitution and decrease yield,
especially for SN1 processes
10
Zaitsev’s Rule for Elimination

Reactions
 In the elimination of HX from an alkyl halide, the more
highly substituted alkene product predominates
11
Mechanisms of Elimination
Reactions
 Ingold nomenclature: E – “elimination”
 E1: X- leaves first to generate a carbocation
 a base abstracts a proton from the carbocation
 E2: Concerted transfer of a proton to a base and
departure of leaving group
12
Elimination Reaction: Zaitsev’s Rule
Elimination reactions can take place by different
mechanisms
• E1, E2, and E1cB reactions
– Differ in the timing of C-H and C-H bond breaking
– All three mechanisms occur in laboratory
– E1cB predominates in biological pathways

10.12 The E1 and E1cB
The E1 Reaction Reactions
• A unimolecular elimination reaction in which
the C-X bond breaks before the C-H bond,
giving a carbocation intermediate
• Analogous to
the SN1 reaction
• Two steps are
involved in the
reaction, the
first of which is
rate-limiting
• Carbocation
intermediate is
present
The E1 and E1cB Reactions

E1 elimination begins with the same unimolecular dissociation as
in the SN1 reaction, but dissociation is followed by loss of H+
from the adjacent carbon rather than by the substitution
E1 and SN1 reactions normally occur together whenever an alkyl
halide is treated in a protic solvent with a nonbasic nucleophile
• The best E1 substrates are also the best SN1 substrates and
mixtures of substitution and elimination products are usually
obtained
• When 2-chloro-2-methylpropane is warmed to 65ºC in 80%
aqueous ethanol, a mixture results
E1 mechanisms are supported by
evidence
• E1 reactions show first-order kinetics, consistent
with a rate-limiting, unimolecular dissociation
process
• E1 reactions show no deuterium isotope effect
– Rupture of the C-H (or C-D) bond occurs after the
rate-limiting step rather than during it
• There is no geometric requirement on the E1
reaction
– The halide and the hydrogen are lost in separate
steps

The E1cB Reaction
• A unimolecular elimination reaction in which the C-H bond
breaks before the C-X bond, giving a carbanion intermediate
– The anion formed expels a leaving group on the adjacent
carbon
• Common in substrates that have a poor leaving group, such
as –OH, two carbons removed from a carbonyl group, HO-C-
CH-C=O
– Poor leaving group disfavors alternative E1 and E2 reactions
– The carbonyl group makes the adjacent hydrogen unusually
acidic by resonance stabilization of the anion intermediate
10.13 Biological Elimination Reactions
All three elimination reactions – E1, E1cB, and

E2 – occur in various biological pathways
• E1cB mechanism is particularly common
– 3-hydroxy carbonyl compounds are frequently
converted to conjugated unsaturated carbonyl
compounds by elimination reactions
– The substrate is usually an alcohol and the H
atom is usually adjacent to a carbonyl group, just
as in the laboratory
Biological Elimination Reactions

• Biosynthesis of fats
– A 3-hydroxybutyryl thioester is dehydrated to the
corresponding unsaturated (crotonyl) thioester
NOW REMEMBER - that the stability of carbanions is:
< < <
C hapter 6 94
In reality there is a spectrum of reaction mechanisms!!
The transition states look like -
“pure” “pure”
E1cb E1
E2
Hofmann Saytzeff
So if L is a strongly electron withdrawing group -

e. g. -F or -N(NMe)3
then a E1cB or E2 with”E1cB-like” character is favored.
C hapter 6 93
K.I.S.S. THE MOST BASIC STUFF
alkyl halide + strong base + heat = E2
alkyl halide + solvent + heat (solvolysis) = E1
alcohol + strong acid + heat = E1 (acid assisted)
O X
typical situation for E1cb
C C C
H next to C=O (easy to remove)
H X = strong base (difficult to break bond)
Only E1 reactions have rearrangements (carbocations)
Only E2 reactions require anti-coplanar b -hydrogens

THE BIG PICTURE
special alkyl halides alcohols
E1cb E2 E1 E1 E1 acid
assisted
strong strong weak acidic

neutral
base base base
stepwise - concerted stepwise - carbocation

carbanion
stereospecific
anti-coplanar “solvolysis”
special case -
not common Zaitsev if not stereospecific
stereochem
requires:
allows
acidic H and Zaitsev Zaitsev Zaitsev
poor leaving Hofmann if
bulky groups
group
a -elim. if no b -H carbocation rearrangements

STEREOCHEMISTRY OF E1CB MECHANISM
Ellimination can also occur by a mechanism known as the E1cb mechansim. The
elimination first-order carbanion mechansim is used to explain the results of some
elimination reactions in which a highly polar leaving group is present and the least
substituted alkene is the major product. But only few studies have actually proven the E1cb
process. The kinetics of the E1cb process are shown below. The reaction is actually not
first order but the slow step is the elimination from S-, a first order step in the process.
Syn elimination often occurs and it is associated with poor leaving groups or theabsence of an
anti-beta hydrogen. The bicyclic compound shows syn elimination becauseno anti beta hydrogen
is available because of the geometry of the system. In open chain
compounds, leaving groups such as +NR3 and F show strong tendencies for synelimination
especially in long chain carbon systems
Reactions that produce stabilized carbanions adjacent to poor leaving groups provide
the best evidence for the E1cb process. The elimination of quaternary ammoniums salts,
also called Hoffmann elimination, is believed to follow a carbanion process with syn
elimination and the formation of the least substituted alkene
When reactions show E1cb character they generally produce the least
substitued alkene as the major product. This occurs because carbanion stability is of the
order: primary> secondary > tertiary. In the example below the major product comes from
the carbanion formed at the secondary carbon atom.
The cis and trans 1-fluoro-2-bromocyclohexane isomers follow different elimination

paths. The trans isomer has an anti-beta hydrogen available for elimination and the reaction
proceeds with tert-butoxide. The cis isomer must use a syn hydrogen in the E1cb process
that causes loss of HF, and requires amide as a stronger base.
Evidence of a Borderline Region between E1cb and E2 Elimination
Reaction Mechanisms: A Combined Experimental and Theoretical
Study of Systems Activated by the Pyridine Ring
Evidence of a Borderline Region between E1cb and E2 Elimination Reaction Mechanisms: A

Combined Experimental and Theoretical Study of Systems Activated by the Pyridine Ring ... The
systems investigated represent borderline cases, where it is uncertain whether the reaction
proceeds via a carbanion intermediate (E1cb, AxhDH + DN) or via the concerted loss of a proton and
the halide (E2, ANDEDN) upon base attack. ... The comparison indicates an E1cb irreversible
mechanism with F, but the deviation observed with Cl and Br does not allow a conclusive
assignment
Catalysis of the β-Elimination of HF from Isomeric 2-

Fluoroethylpyridines and 1-Methyl-2-fluoroethylpyridinium Salts.
Proton-Activating Factors and Methyl-Activating Factors as a
Mechanistic Test To Distinguish between Concerted E2 and E1cb
Irreversible Mechanisms
Proton-Activating
Factors and Methyl-Activating Factors as a Mechanistic Test To Distinguish between Concerted E2
and E1cb Irreversible Mechanisms ... The high values of MethylAF are in agreement with an
irreversible E1cb mechanism (ANDE* + DN) for substrates 5 and 7 and with the high stability of the
intermediate carbanion related to its enamine-type structure. ... These high PAF values are
indicative of an irreversible E1cb mechanism rather than a concerted E2 (ANDEDN) mechanism. ...
Negative Ion Hyperconjugation and Its Relevance to the Mechanism of E1cB Reactions.
An ab Initio Study
Negative Ion Hyperconjugation and Its Relevance to the Mechanism of E1cB Reactions. ... Some
time ago I proposed that E2 and E1cB(irrev) mechanisms could be distinguished by the observation
of a leaving group isotope effect or element effect in the former but not in the latter case. 1 This
argument assumes that there is no weakening of the bond to the leaving group in the rate-
determining proton transfer of the E1cB reaction. ... This is the kind of transition structure one
would expect for a concerted E2 but not for an E1cB mechanism! ...
Large, inverse solvent isotope effects: a simple test for the E1cB mechanism
Large, inverse solvent isotope effects: a simple test for the E1cB mechanism ... Proton-Activating
Factors and Methyl-Activating Factors as a Mechanistic Test To Distinguish between Concerted E2
and E1cb Irreversible Mechanisms ... Proton-Activating Factors and Methyl-Activating Factors as a
Mechanistic Test To Distinguish between Concerted E2 and E1cb Irreversible Mechanisms
Ab Initio Molecular Dynamics Simulations of Elimination Reactions in

Water Solution: Exploring the Borderline Region between the E1cb and
E2 Reaction Mechanisms
We report a theoretical study, based on ab initio molecular dynamics simulations in water
solution, of the mechanism of base-induced β-elimination reactions in systems activated by the
pyridyl ring, with halogen leaving groups. The systems investigated represent borderline cases,
where it is uncertain whether the reaction proceeds via a carbanion intermediate (E1cb, AxhDH +
DN) or via the concerted loss of a proton and the halide (E2, A NDEDN) upon base attack. Recent
theoretical and experimental evidence points toward the lack of a net distinction between the
E1cb and E2 reaction paths, which seem to merge smoothly into each other in these borderline
cases (Alunni, S.; De Angelis, F.; Ottavi, L.; Papavasileiou, M.; Tarantelli, F. J. Am. Chem. Soc.
2005, 127, 15151−15160). In this study, we explore the dynamics on the potential energy surface
for the reaction of 2-(2-fluoroethyl)-1-methyl pyridinium with OH - by means of Car−Parrinello
simulations in water solution. Our results indicate that the reaction mechanism effectively evolves
through the potential energy region of the carbanion: the carbon−fluoride bond breaks only after
the carbon−hydrogen bond, confirming the conclusions of a recently reported study of the
potential energy surface for this system.
Ketene-Forming Eliminations from Aryl Phenylacetates Promoted by
R2NH/R2NH2+ in Aqueous MeCN. Mechanistic Borderline between E2 and
E1cb
Elimination reactions of 2-X-4-NO2C6H3CH2C(O)OC6H3-2-Y-4-NO2 [X = H (1), NO2 (2)] promoted

by R2NH/R2NH2+ in 70 mol % MeCN(aq) have been studied kinetically. The base-promoted
eliminations from 1 proceeded by the E2 mechanism when Y = Cl, CF3, and NO2. The
mechanism changed to the competing E2 and E1cb mechanisms by the poorer leaving groups
(Y = H, OMe) and to the E1cb extreme by the strongly electron-withdrawing β-aryl group (2, X
= NO2). The values of β = 0.14 and |βlg| = 0.10−0.21 calculated for elimination from 1 (Y =
NO2) indicate a reactant-like transition state with small extents of proton transfer and C α−OAr
bond cleavage. The extent of proton transfer increased with a poorer leaving group, and the
degree of leaving group bond cleavage increased with a weaker base. Also, the changes in the
k1 and k-1/k2 values with the reactant structure variation are consistent with the E1cb
mechanism. From these results, a plausible pathway of the change of the mechanism from E2
to the E1cb extreme is proposed.
Borderline between E1cB and E2 Mechanisms. Chlorine Isotope Effects

in Base-Promoted Elimination Reactions
The chlorine leaving group isotope effect has been measured for the base-promoted elimination
reaction of 1-(2-chloro-2-propyl)indene (1-Cl) in methanol at 30 °C: k35/k37 = 1.0086 ± 0.0007 with
methoxide as the base and k35/k37 = 1.0101 ± 0.0001 with triethylamine (TEA) as the base. These
very large chlorine isotope effects combined with large kinetic deuterium isotope effects of 7.1
and 8.4, respectively, are consistent not with the irreversible E1cB mechanism proposed
previously (J. Am. Chem. Soc. 1977, 99, 7926) but with the E2 mechanism with transition states
having large amounts of hydron transfer and very extensive cleavage of the bond to
chlorineBorderline between E1cB and E2 Mechanisms. ... These very large chlorine isotope effects
combined with large kinetic deuterium isotope effects of 7.1 and 8.4, respectively, are consistent
not with the irreversible E1cB mechanism proposed previously (J. Am. ... Kinetic Isotope Effects
for an E1cB Reaction with Internal Return
The Mechanism of Base-Promoted HF Elimination from 4-Fluoro-4-(4-

nitrophenyl)butan-2-one Is E1cB. Evidence from Double Isotopic
Fractionation Experiment
s
The Mechanism of Base-Promoted HF Elimination from 4-Fluoro-4-(4-nitrophenyl)butan-2-one Is
E1cB. ... This new data clearly demonstrates that the elimination proceeds via an E1cB
mechanism. ... These results rule out an E1 mechanism in which the rate-limiting detachment of
the leaving group precedes a fast proton-transfer step but are consistent with a rate-limiting bond
breakage of the proton being transferred in either a concerted E2 or a stepwise E1cB mechanism
Change in Rate-Determining Step in an E1cB Mechanism during

Aminolysis of Sulfamate Esters in Acetonitrile
The kinetics of the reactions of the nitrogen−sulfur(VI) esters 4-nitrophenyl N-methylsulfamate
(NPMS) with a series of pyridines and a series of alicyclic amines and of 4-nitrophenyl N-
benzylsulfamate (NPBS) with pyridines, alicyclic amines, and a series of quinuclidines have been
investigated in acetonitrile (ACN) in the presence of excess amine at various temperatures.
Pseudo-first-order rate constants (kobsd) have been obtained by monitoring the release of 4-
nitrophenol/4-nitrophenoxide. From the slope of a plot of kobsd vs [amine], second-order rate
constants (k‘2) have been obtained for the pyridinolysis of NPMS, and a Brønsted plot of log k‘2 vs
pKa of pyridine gave a straight line with β = 0.45. However, aminolysis with alicyclic amines of
NPMS gave a biphasic Brønsted plot (β1 = 0.6, β2 ≈ 0). Pyridinolysis and aminolysis with alicyclic
amines and quinuclidines of NPBS also gave similar biphasic Brønsted plots. This biphasic behavior
has been explained in terms of a mechanistic change within the E1cB mechanism from an
(E1cB)irrev (less basic amines) to an (E1cB)rev (more basic amines), and the change occurs at
approximately the pKa's (in ACN) of NPMS (17.94) and NPBS (17.68). The straight line Brønsted
plot for NPMS with pyridines occurs because the later bases are not strong enough to substantially
remove the substrate proton and initiate the mechanistic change observed in the reaction of
NPMS with the strong alicyclic amines and quinuclidines. An entropy study supports the change
from a bimolecular to a unimolecular mechanism. This is the first clear demonstration of this
E1cB mechanistic changeover involving a nitrogen acid substrate.
APPLICATIONS:
Irreversible Inhibitors of Serine, Cysteine, and Threonine Proteases

The LC-MS and tryptic digest analysis shows elimination of the bromide ion and covalent bond
formation between the enzyme active site Cys 148 and the inhibitor. ... An alternative is the
isocyanate (E1cb) mechanism (Figure 81, pathway a).
Iminium Catalysis
The iminium-activated reaction will be catalytic only if the amine catalyst is released in the final
hydrolysis or elimination step. ... If intermediate 449 is treated with triethylamine and a drying
agent instead of K2CO3, a molecule of water is eliminated by an E1cB mechanism, yielding the
condensation product 450. ...
Synthesis of Cyclopentitols by Ring-Closing Approaches

A one-pot sequential process, involving allylation, free-radical cyclization, and elimination for the
preparation of multifunctional carbocycles possessing exo methylene unit, has been developed. ...
The authors have suggested that the latter was caused by decomposition of the precursor
dialdehyde 326 by E1cB elimination of the acetal protecting group. ...
A synthesis of the ABC framework of dumsin is described. The optically active intermediate 9b,
which is expeditiously assembled from 5-oxobornyl pivalate by the sequential implementation of
an oxy-Cope rearrangement and an intramolecular ene reaction, proved to be suitably
functionalized for ultimate conversion to 5. The synthesis plan relies on two approaches to this
targeted intermediate. In the first, the exocyclic double bond introduced during EtAlCl 2-promoted
closure of aldehyde 10b is cleaved to leave a carbonyl group that is amenable to hydride
reduction and elimination of water. Cleavage of the resulting double bond with ruthenium
tetroxide provided the seco ketoacid. The same advanced intermediate was obtained by initially
positioning the double bond internal to the five-membered ring in advance of transient ring
expansion via diketone formation and intramolecular aldolization. Both of these approaches
bypass the complications arising from the substantial steric congestion prevailing in these
structural networks. The task of covalently positioning an oxygen atom adjacent to the gem-
dimethyl-substituted carbon in 5 was properly realized by oxidative decarboxylation. The
stereochemical assignments to many of the intermediates were confirmed by an X-ray
crystallographic analysis of
In the first, the exocyclic double bond introduced during EtAlCl 2-promoted closure of aldehyde
10b is cleaved to leave a carbonyl group that is amenable to hydride reduction and elimination of
water. ... The assumption was made that the syn elimination envisaged for 37 (Scheme 7) would
not prove problematic in light of the possible operation of the E 1cb mechanistic option. ...
Total Syntheses of Epothilones B and D
Total syntheses of the microtubule stabilizing antitumor drugs epothilone B and D are described,
starting from optically pure (S)-malic acid and methyl (R)-3-hydroxy-2-methylpropionate.
Obviously, anion 21a had undergone an intramolecular proton shift followed by an E1cB
elimination
Syntheses of gem-Dihalocyclopropanes and Their Use in Organic

Synthesis
In a now classic paper from 1954, Doering and Hoffmann showed that dichlorocarbene generated
from chloroform in an α-elimination process under strictly anhydrous conditions adds to alkenes
with the formation of gem-dichlorocyclopropane derivatives.1 To date, the addition of
dihalocarbenes to alkenes is the most important and, in fact, the only synthetic route to gem-
dihalocyclopropanes. ... The formation of cyclopropylidene dimers can occur via a direct reaction
of two molecules of the halolithium carbenoid, with simultaneous extrusion of two molecules of
lithium bromide, or via a stepwise formation of the intermediate β-halobicyclopropyllithium,
followed by an E1cb elimination reaction (eq 93). ...
Synthesis and Reactivity of sp3-Geminated Organodimetallics
However, the use of an ether moiety instead of an alcoholate as a leaving group allows the
quantitative formation of an olefinated product 20 via an E1CB mechanism (Scheme 7). ... An
alternative method has been recently developed 21 for the synthesis of olefins via a double
alkylation followed by a Ramberg−Bäcklund elimination
Structure-Based Design, Synthesis, and Biological Evaluation of

Inhibitors of Mycobacterium tuberculosis Type II Dehydroquinase
The final step is the acid-catalyzed elimination of the C1 hydroxyl group catalyzed by His101. ...
Scheme 2. Proposed E1CB Mechanism for the Enzymatic Conversion of 3-Dehydroquinic Acid (1) to
3-Dehydroshikimic Acid (2) Catalyzed by Type II Dehydroquinase Indicating the Residues Involved
in the Catalysis ...
Novel 2,5-Hexanedione Analogues. Substituent-Induced Control of the Protein

Cross-Linking Potential and Oxidation Susceptibility of the Resulting Primary
Amine-Derived Pyrroles
The selective oxidation of the enolizable acetoacetamides by Mn(III) or Ce(IV), subsequent free
radical addition to isopropyl acetate, and facile elimination of acetyl radical from the
acetoxyalkyl adduct radical are believed to be involved (30) in this simple one-step synthesis of γ-
diketones 9 and 10. ... These side products reflect an E1cb elimination reaction that competes
with pyrrole formation, resulting in the generation of adducts comprised of one molecule of 3 and
two molecules of amine, thereby explaining the observed protein cross-linking
1-Bromo-1-lithioethene: A Practical Reagent in Organic Synthesis
Ketone 10a is usually quite susceptible to E elimination ... 28

However, no traces of such elimination byproducts could be
1cb
detected in the crude reaction mixture (by 1H NMR analysis) when 10a was allowed to react with
1. ... An efficient one-pot method for bromination−elimination ...
Identification of 3-Hydroxykynurenine Bound to Proteins in the Human

Lens. A Possible Role in Age-Related Nuclear Cataract†
It is likely that each adduct undergoes elimination via an E1cb mechanism, although the reasons
for the differences in stability are unclear. ...
Chiral Inversion and Hydrolysis of Thalidomide: Mechanisms and Catalysis by Bases

and Serum Albumin, and Chiral Stability of Teratogenic Metabolites
For four albumin concentrations, the observed pseudo-first-order rate constants of chiral inversion
k(R-to-S) and k(S-to-R) as well as those of hydrolysis were estimated by fitting of a two-compartment
kinetic model with elimination from both compartments to the measured concentrations of (R)-
and (S)-thalidomide during incubation of either enantiomer. ... In theory, hydrolysis might also
occur via an E1cb mechanism and a ketene intermediate stemming from the same carbanion
involved in chiral inversion and deuterium exchange.
Kinetics and Mechanism of Hydrolysis of N-Acyloxymethyl Derivatives

of Azetidin-2-one
The pH−rate profiles of 6a−g also differ significantly from those for simple ester hydrolysis, which
occurs via an addition−elimination mechanism and usually exhibits the incursion of specific base
catalyst at ph6-7The
Transformation of Arylmethylamines into α-Aminophosphonic Acids via
Metalated Phosphoramidates: Rearrangement of Partly
Configurationally Stable N-Phosphorylated α-Aminocarbanions
Its formation starts very likely with the generation of imine 19 by elimination (E2 or E1cB) of p-
toluenesulfinate from 6b. ... LDA did not effect elimination of p-toluenesulfinate, but metalation
of the p-tolyl ring ortho to the sulfonyl group
Tandem Nitroaldol−Dehydration Reactions Employing the Dianion of

Phenylsulfonylnitromethane1
An E1cb pathway for the formation of the α,β-unsaturated α-nitrosulfone has been considered,
but no supporting evidence has been obtained for it. ... The scope of the tandem
nitroaldol−elimination sequence was next investigated by examining a series of aldehydes
A Reductive Cyclization Approach to Attenol A
. ... 24 Loss of the homoallylic silyl ethers, presumably through E1 cb elimination, was evident in the
1
H NMR spectrum of the crude reaction mixtures. ... The lithiated sulfone was quenched with
PhSSO2Ph,26 and Et3N was introduced into the reaction vessel to scavenge the benzenesulfinic acid
generated in the elimination reaction
A Conformationally Locked Analogue of the Anti-HIV Agent Stavudine.
An Important Correlation between Pseudorotation and Maximum
Amplitude
This important intermediate was to be obtained from the readily accessible 5-(benzyloxymethyl)-
4-(benzyloxy)bicyclo[3.1.0]hexan-2-ol (3),5 following a sequence designed to give the olefin after
elimination of the C4-OH (Scheme 1). ... The optimized yield for this reaction was only 51%,
possibly reflecting the less than ideal geometry (Figure 2C) that forces elimination via a two-step
process (E1cB mechanism
Synthesis and Structural Analysis of the Anilides of Glucuronic Acid and

Orientation of the Groups on the Carbohydrate Scaffolding
The coupling of 7 with aniline in the presence of ethyl chloroformate and triethylamine 13 produced
the 4,5-unsaturated amide 11 as a result of the base-promoted elimination of acetic acid in
addition to the amide formation.
Kinetics of Polymerization Reaction of α,α‘-Bis(tetrahydrothiophenio)-p-xylene

Dichloride
From these results, an elimination−free radical polymerization mechanism is proposed. ... The
result is consistent with the (E1cb)rev mechanism in which the departure of the leaving group is
rate-limiting.
The Stereoselective Synthesis of 4‘-β-Thioribonucleosides via the Pummerer Reaction

A likely explanation for the observed difference in the reaction of R-10 and S-10 is that the reaction proceeds via an E2 type pathway, which prefers anti elimination. ...
24
Depending on the structures of the starting sulfoxides, both E1cb and E2 type pathways are
known to give the α-thiocarbocation intermediates from sulfoxides. Design, Synthesis,
and In Vitro Testing of α-Methylacyl-CoA Racemase Inhibitors
We envisaged that elimination of fluoride from the proposed enolate by an E1cB mechanism
within the active site would generate an α,β-unsaturated thioester that may then undergo attack
by an active site base or nucleophile to give the inactivated enzyme. ... The fluorination proved
to be particularly low yielding (20%), a consequence of the propensity for elimination of fluoride,
which could be limited at low temperature
A General Acid-Catalyzed Anion Breakdown Associated with an E1cB Reaction in the

Hydrolysis of Aryl N-(Substituted Phenylsulfonyl)carbamates
A General Acid-Catalyzed Anion Breakdown Associated with an E1cB Reaction in the Hydrolysis of
Aryl N-(Substituted Phenylsulfonyl)carbamates ...
Carbonion (ElcB)mechanism of ester hydrolysis. I. Hydrolysis of malonate esters
Mechanistic Borderline between E2 and E1cb ... Elimination reactions of 2-X-4-

NO2C6H3CH2C(O)OC6H3-2-Y-4-NO2 [X = H (1), NO2 (2)] promoted by R2NH/R2NH2+ in 70 mol %
MeCN(aq) have been studied kinetically. ...
Synthesis of an Estrogen Receptor β-Selective Radioligand: 5-

[18F]Fluoro-(2R*,3S*)-2,3-bis(4-hydroxyphenyl)pentanenitrile and
Comparison of in Vivo Distribution with 16α-[18F]Fluoro-17β-estradiol
It is of note that the fluorine analogue of DPN itself, 3-fluoro-2,3-bis(4-
hydroxyphenyl)propanenitrile, was not selected because it was expected to undergo rapid
defluorination under physiological conditions by a facile elimination mechanism. ... (23) Ryberg, P.; Matsson,
O. The Mechanism of Base-Promoted HF Elimina
tion from 4-Fluoro-4-(4-
nitrophenyl)butan-2-one Is E1cB. ...
Synthesis of Five-, Six-, and Seven-Membered Heterocycles by Intramolecular Ring

Opening Reactions of 3-Oxetanol Derivatives
Desilylation (K2CO3, MeOH) to diol 17 is facile, but it should be noted that 17 is prone to an
elimination to benzofuran 19. ... Silyl ether 20 or the alkoxide 21, however, are forced to
undergo an elimination with excess base by an E2 or E1cB pathway. ...
The carbanion mechanism (ElcB) of ester hydrolysis. III. Some structure-reactivity

studies and the ketene intermediate

MeCN(aq) have been studied kinetically. ...
Synthesis of Methylene- and Alkylidenecyclopropane Derivatives
The cyclopropanation of allene itself gives poor results, 40-42 but the addition of dichloro- or
dibromocarbene generated in several ways (base-induced elimination from CHX3 or
trihaloacetate, thermal decomposition of phenyl(trihalomethyl)mercury or
trichloromethyltrifluorosilane) to 1,1-disubstituted allenes afforded MCPs 44 in high yields
(Scheme 10). ... Treatment of bromoalkenes with bases (KOt-Bu) is not as effective as the previous treatments with allyl bromides, producing always mixtures of
elimination products besides ACPs and MCPs. ... The double Michael addition of malonate on trichloronitroethylene followed by double HCl elimination produced a
functionalized ACP in 34% yield.
Synthesis of Enantiomerically Pure 1,2-Diamine Derivatives of 7-

Azabicyclo[2.2.1]heptane. New Leads as Glycosidase Inhibitors and
Rigid Scaffolds for the Preparation of Peptide Analogues
These results can be interpreted in terms of two competitive processes: the desired SN2
displacement of endo-mesylate 14 by the azide anion and the β-elimination of methanesulfonic
acid from 14 induced by the basic medium (fluoride anion-induced E 1cb elimination) and producing
intermediate alkene 17. ... This is consistent with the intervention of an SN2 displacement process
that is retarded less at lower temperatures than the elimination process (Scheme
3). ...Glutathione-Dependent Metabolism of the Antitumor Agent Sulofenur. Evidence for
the Formation of p-Chlorophenyl Isocyanate as a Reactive Intermediate
Since decomposition of carbamate thioester conjugates in aqueous media is known to take place
primarily via a base-catalyzed elimination E1cb reaction (37), the GSH conjugate, SCPG, can be
expected to be even more unstable in the basic environment of bile than in neutral solution. ...
Most likely, depletion of substrate and product reflects elimination from each conjugate of CPIC,
which undergoes hydrolysis and subsequent decarboxylation. ... However, this low molecular mass
(127 Da) aniline derivative may serve as a useful indicator of metabolic flux through the
isocyanate pathway, although it should be recognized that its excretion into bile would reflect the
aggregate of direct hydrolysis and elimination of the parent diarylsulfonylureas. ...
Generation, Stability, and Reactivity of Small, Multiply Charged Ions in the Gas Phase
For example, the competition of substitution and elimination in the reactions of nucleophiles Y-
with alkyl halides (e.g., RCH2CH2X) according to reactions 6a and 6b formed the subject of
numerous studies. ... This reaction proceeds via an E1cB mechanism which involves a net
cancellation of charges, i.e., an anion and a cation only yield neutral products.
Total Syntheses, Fragmentation Studies, and

Antitumor/Antiproliferative Activities of FR901464 and Its Low
Picomolar Analogue
FR901464 is
Facile epoxide opening by β-elimination gave two enones, one of which could undergo
dehydration via its hemiketal to form a furan. ... We speculate that the low yields for these
reactions are due to an intramolecular deprotonation−elimination pathway; the alkoxide
generated after addition to the aldehyde can intramolecularly deprotonate a hydrogen atom at C2
and induce an E1cb reaction
Role of Y94 in Proton and Hydride Transfers Catalyzed by Thymidylate Synthase
This is followed by the release of H4folate from the ternary complex (step 5, E1CB mechanism)
(13) which generates the exocyclic methylene intermediate (E). ... (ii) The abstraction of the
proton from C5 of dUMP involves E2 elimination of C146 (step 4‘). ...
Effects of Altering the Electronics of 2-Methoxyestradiol on Cell
Proliferation, on Cytotoxicity in Human Cancer Cell Cultures, and on
Tubulin Polymerization
Application of Base Cleavable Safety Catch Linkers to Solid Phase

Library Production
The sulfone resins are then cleaved by β-elimination in the gas phase or in solution by secondary
amines to produce acids and primary, secondary, or tertiary amines. ... In general, cleavage rates
were pseudo first order in substrate and consistent with the accepted E1cB mechanism,17 a
potentially reversible deprotonation followed by an E1 elimination, and were correlated with the
leaving group ability. ...
Kinetics and Mechanism of the Benzenethiolysis of 2,4-Dinitrophenyl
and 2,4,6-Trinitrophenyl Methyl Carbonates and S-(2,4-Dinitrophenyl)
and S-(2,4,6-Trinitrophenyl) Ethyl Thiolcarbonates
Although it is known that ArO- is a better nucleofuge compared to an isobasic Ar‘S-, as judged by
elimination rate constants from the conjugate bases of the corresponding esters (E1cB
mechanism),17 presumably the rate constant k2 (DNPO- expulsion from 2) is not greater than k-1
(isobasic Ar‘S- expulsion from 2). ...
An Unexpected Highly Stereoselective Double Aza-Baylis−Hillman

Reaction of Sulfonated Imines with Phenyl Vinyl Ketone
Moreover, the subsequent elimination (E2 or E1cB) from the betain intermediate (nitrogen and
phosphane betain) should also have some differences (Figure 2, C and D). ...
Regioselectivity and the Nature of the Reaction Mechanism in
Nucleophilic Substitution Reactions of 2,4-Dinitrophenyl X-Substituted
Benzenesulfonates with Primary Amines
In fact, an upward curvature in the Hammett plots has often been reported for nucleophilic
substitution reactions of the benzylic system or those of various carboxylic esters (e.g.,
substituted phenyl esters of 4-nitrophenylacetic acid) in which a change in reaction mechanism
occurs from SN1 to SN2 for the former case and from a bimolecular reaction (either one step or a
stepwise addition−elimination mechanism) to an E1cB mechanism for the latter
case. ...Elucidation
of the Electron Transfer Reduction Mechanism of
Anthracene Endoperoxides
elimination mechanism and formation of PPA. ... According to the mechanism in Scheme 2, protonation of the alkoxide anion portion is required for elimination of
hydroxide and formation of PPA. ... 79

Evidence for the slow protonation of the carbanion was verified with the
different acids chosen, and the results illustrated in Figure 3 indicate preferential kinetic
protonation of the alkoxide anion that leads to the formation of PPA via an E1CB-type elimination.
The Aminobarbituric Acid−Hydantoin Rearrangement

Fragmentation of aminobarbituric acids was not uniform but depended on the amino residue
introduced at position 5.25-28 For 5-carbamoyl hydantoins, the elimination of R2NCO was the
significant fragmentation29,34 accompanied by further decay that included the substituent at
position 1.30-33 ... Alternatively, the formation of hydantoins 4 followed an elimination−addition
mechanism, known from E1cB processes in acyl transfer reactions. ...
Carbanionic Reactivity of the Anomeric Center in Carbohydrates
Having a good leaving group in the β-position to the anionic center a glycosyl anion may undergo
an E1cB elimination to give glycals VIII. ... On the other hand, elimination of an oxide or hydride,
which is known with simple carbanions, 43 has rarely been observed with glycosyl anions,
presumably because of the slight stabilizing effect of the ring oxygen. ... On the basis of
deuteration experiments, it was suggested that the reaction proceeded through an E2 rather than
the expected E1cB mechanism. ...
Evolution of Enzymatic Activity in the Enolase Superfamily: Functional

Studies of the Promiscuous o-Succinylbenzoate Synthase from
Amycolatopsis†
Subsequent structural studies of the catalytically inactive K133R mutant (14) revealed the
absolute configuration of the SHCHC substrate and lead to the conclusion that the dehydration
reaction to form the OSB product necessarily proceeds via a syn elimination reaction in which Lys
133 at the end of the second β-strand is the only acid/base catalyst, first abstracting the α-proton
and then, as the conjugate acid, facilitating departure of the hydroxide leaving group. ...
Accordingly, in analogy with the mechanism of the OSBS from E. coli (14), we propose that this
reaction proceeds via an E1cb mechanism in which α-proton abstraction of SHCHC by Lys 163
forms a Mn2+-stabilized enediolate anion intermediate that collapses to OSB with the assistance of
the conjugate acid of Lys 163 (Figure 2A). Lys 263 likely forms a π-cation interaction with the
SHCHC substrate, with this interaction enhanced as negative charge develops as the intermediate
is formed by abstraction of the α-proton. ...
Termination and Transfer Reactions in the Group Transfer
Polymerizations of Acrylates Catalyzed by Mononuclear Early d-Block
and f-Block Metallocenes: A DFT Study
The proposed mechanism amounts to a Dieckmann condensation (Claisen intramolecular

condensation), and it leads to elimination of a MeOH molecule and formation of an unreactive
product containing a substituted cyclohexanone ring, as illustrated in Scheme 2. ... The second
mechanistic possibility is that a two-step elimination occurs, following an E1cB mechanism. ...
Conformational Dynamics along an Enzymatic Reaction Pathway: Thymidylate

Synthase, “the Movie”
The trans-diequatorial arrangement would permit a concerted elimination of the cofactor and H-
C5 from dUMP, and would orient the transferred methylene group in a manner consistent with the
stereospecificity of hydride transfer (22, 23). ... In particular, they show that the stereospecificity
of hydride transfer can be ascribed to a two-step (E1CB) elimination of first, dUMP H-C5 and then
the cofactor from intermediate II, a mechanism which does not require conversion of the trans-
diaxial orientation of the catalytic sulfhydryl and methylene bridge to a trans-diequatorial
arrangement. ...
Biodegradable Hydrogels for Time-Controlled Release of Tethered
Peptides or Proteins
To demonstrate the elimination of attached PEG chains, 100 μL of this solution were diluted with
900 μL of 50 mM borate buffer, pH 9.0, and incubated for 24 h at 50 °C. ... These carbamates
hydrolyze in neutral and basic solutions by an E1cB elimination reaction involving the
intermediate formation of an unstable isocyanate.
Reduction of Oxamyl and Related Pesticides by FeII: Influence of Organic Ligands and
Natural Organic Matter
Pseudo-first-order rate constants for the reduction (kred, h-1) and E1cb elimination (kelim, h-1) of
oxamyl and methomyl were determined for each batch reaction using data for both parent
compound disappearance and reaction product appearance according to a procedure outlined
previously (25) (details provided in the Supporting Information). ... In addition, the organic ligands
have no effect on the rates of a parallel E1cb elimination reaction (discussed in detail in ref 24).
Extended ElcB mechanism for ester hydrolysis: allylic substitution via carbanion in
ester hydrolysis

MeCN(aq) have been studied kinetically
Tight Binding Inhibitors of Scytalone Dehydratase: Effects of Site-Directed Mutations
Off and on the enzyme, scytalone undergoes E1cb-like dehydration reactions that are
differentiated by the greater commitment to product formation (elimination) following
enolization in the enzyme-catalyzed reaction (
Some Items of Interest to Process R&D Chemists and Engineers
Using Pd-based catalysts, the low yields observed in the coupling of certain substrates have been
attributed to the slow rate of C−O reductive elimination relative to β-hydride elimination from
the LnPdII(Ar)(alkoxide) intermediate. ... The use of KOPh as an additive is significant in
determining the outcome of the process since in the absence of this base, the initial product of
oxidative insertion undergoes direct reaction with the ester carbonyl to yield a 2,3-
dihydroquinolin-4-one. The researchers reasoned that addition of a basic species would serve to
enolize the ester, but the potential for elimination of the aniline fragment via an E1cB
mechanism steered them from the use of stronger bases such as KOtBu. Depending on the
substrate, indolines can sometimes be isolated from this reaction, but in most cases these convert
directly to indoles under the reaction conditions.
Crystal Structure of a Sulfur Carrier Protein Complex Found in the

Cysteine Biosynthetic Pathway of Mycobacterium tuberculosis
This topology is consistent with other β-elimination enzymes (37). ... This suggests an E1cB
mechanism rather than an E2 mechanism for this elimination reaction, which occurs with trans
stereochemistry. ...
Amidates as Leaving Groups: Structure/Reactivity Correlation of the

Hydroxide-Dependent E1cB-like Breakdown of Carbinolamides in
Aqueous Solution
In fact, carbinolamides exhibit a form of reactivity in water wherein the amide portion of their
structure acts as a leaving group in what could be formally described as an elimination reaction
(see Scheme 1). ... Previous studies investigating (E1cB)R reactions where an amidate acted as a leaving group were shown to undergo relatively slow rate
determining departure of N-methylacetamidate in ethanol in the presence of ethoxide (k = 4.6 × 10-6 s-1 for PhSO CH CH NHCOCH in EtOH/NaOEt at 25 °C). ...
obsd 2 2 2 3
These studies clearly show that amides are capable of acting as leaving groups in elimination reaction supporting (E1cB) studies performed by Stirling. ...
R
Phosphonylpyrazoles from Bestmann−Ohira Reagent and Nitroalkenes:
Synthesis and Dynamic NMR Studies
According to the proposed mechanism,(30) the nucleophilic base mediated acyl cleavage of BOR 2
followed by cycloaddition of the resulting diazomethylphosphonate anion with nitroalkene 1a
provides initial cycloadduct which undergoes elimination to afford phosphonylpyrazole 3a. ... This
was explained primarily in terms of the elimination of HBr by an E2 mechanism and HNO2 by an
E1cB mechanism from the initial cycloadducts. ... However, in the case of 8b and 8d, a
competing E1cB mechanism is also operative which leads to the formation of a mixture of 9 and
10. ...
Gas-Phase Base-Induced 1,4-Eliminations: Occurrence of Single-, Double-, and Triple-

Well E1cb Mechanisms
Gas-Phase Base-Induced 1,4-Eliminations: Occurrence of Single-, Double-, and Triple-Well E1cb

Mechanisms ... (1R,6R)-2-Succinyl-6-hydroxy-2,4-cyclohexadiene-1-carboxylate (SHCHC) synthase
(MenH) is an α/β fold enzyme containing a catalytically essential serine−histidine−aspartate triad
typical of serine proteases but catalyzes a pyruvate elimination reaction
Mild and Safer Preparative Method for Nonsymmetrical Sulfamides via

N-Sulfamoyloxazolidinone Derivatives: Electronic Effects Affect the
Transsulfamoylation Reactivity
An elimination mechanism (E1cB) of reaction proceeding via the very electrophilic N-

sulfonylamine RN SO2 species was established when sulfamoyl chlorides (RNHSO2Cl) were used to
prepare sulfamides
9-(2-C-Cyano-2-deoxy-β-D-arabino- pentofuranosyl)guanine, a
Potential Antitumor Agent against B-Lymphoma Infected with Kaposi's
Sarcoma-Associated Herpesvirus
Compound 1 is chemically labile in alkaline solution, leading to epimerization and degradation via
the E1cB mechanism to give cytosine. ... However, interestingly, the formation of guanine and 1,4-anhydro-2-C-cyano-2-deoxy-D-erythro-pent-
l-enitol (18, glycal), which were β-elimination products of 3, was more suppressed than that of 1.
Participation of an Extended p-Oxo Ketene Intermediate in the Dissociative Alkaline

Hydrolysis of Aryl 4-Hydroxycinnamates
The alkaline hydrolysis of the title esters, possessing three conjugated units between the internal
nucleophile (the hydroxyl group) and the reaction center, follows an E1cB mechanism involving
the participation of an extra extended p-oxo azoketene ... ... The alkaline hydrolysis of title
esters possessing acidic leaving groups follows an E1cB mechanism involving the participation of
an extra extended p-oxo ketene intermediate. ... Reactivity comparison, Arrhenius parameters,
and trapping of the above-depicted unsaturated intermediate strongly suggest that the alkaline
hydrolysis of the title ester follows a mechanism of the E1cB type.
Tandem Double Intramolecular [4+2]/[3+2] Cycloadditions of

Nitroalkenes. The Fused/Bridged Mode
triethylamine12) were unsuccessful due to partial isomerization of the double bond. ... 20
Thus, it would appear most likely that the
elimination takes place via either an E1cb mechanism or by an E2 mechanism in which the
isomeric nitro acetates can interconvert (Scheme 17). ...
Unusual Mechanism for an Aminomutase Rearrangement: Retention of
Configuration at the Migration Termini
The lyases share a characteristic active site motif, alanine−serine−glycine (ASG), that
autocatalytically rearranges to form a functional 3,5-dihydro-5-methylidene-4H-imidazol-4-one
(MIO) prosthesis acting as a Lewis acid to promote the elimination of NH3 and H+ from the
arylalanine substrate (8). ... The PAL-mediated elimination process begins with removal of the
pro-3S hydrogen likely by the 137His residue of PAL from Rhodosporidium toruloides (17), followed
by E1cb-type displacement of ammonia from the substrate to form trans-cinnamate (15, 17) (Figure
2B). ... Alternatively, the MIO is attacked by the amino group to facilitate Hoffmann-type
elimination of the NH3/H+ (amine comple
Cycloaddition of Alkynyl Ketones with N-Tosylimines Catalyzed by Bu3P

and DMAP: Synthesis of Highly Functionalized Pyrrolidines and
Azetidines
Finally, the proton transfer generates intermediate 10, followed by elimination of Bu3P to
afford the desired product 3 or 4. ... Then, the trans elimination (E1cb type) of DMAP from
14 affords product 5 with E configuration, and regenerates DMAP. ...
Positional Ordering of Reacting Groups Contributes Significantly to the
Efficiency of Proton Transfer at an Antibody Active Site
promoted E2 elimination of
substituted benzisoxazoles (Scheme 1),4,5 also known as the Kemp elimination. ... 7
Mechanistic studies suggest either an E1cb or an
H50
E2 elimination mechanism, in which Glu , the same functional group utilized by 34E4, serves as
the general base
Mechanistic Insights into the Michael Addition of Deoxyguanosine to

Catechol Estrogen-3,4-quinones†
Specifically, the sequence of elimination events, glycosidic bond cleavage and rearomatization of
the estrogen A ring, was explored. ... Reverse Michael addition between pyridine nucleophiles and
Michael acceptors has been shown to proceed via an E1cB mechanism, where proton removal is
the rate-limiting step (37). ...
Steady-State and Laser Flash Photolysis Study of the Carbon−Carbon

Bond Fragmentation Reactions of 2-Arylsulfanyl Alcohol Radical
Cations
Following the language used in β-elimination reactions, to which these fragmentation have been
correctly assimilated,8 these transition states might be indicated as E1cb-like. ... In conclusion,
stereoelectronic effects seem to play a very minor role in the fragmentation of 2-phenylsulfanyl
alcohol radical cations, probably due to a process that, as said before, is shifted to the E1cb side
of the mechanistic spectrum.
Rates of H/D exchange of 9-fluorenyl sulfoxides. Evidence for an irreversible E1cB

mechanism for base-induced sulfine formation from methyl diarylmethanesulfinates
Evidence for an irreversible E1cB mechanism for base-induced sulfine formation from methyl
diarylmethanesulfinates ...
Eliminations in the Reactions Catalyzed by UDP-N-Acetylglucosamine 2-Epimerase
These intermediates are formed by an anti elimination of UDP from UDP-GlcNAc and a syn
elimination of UDP from UDP-ManNAc. ... The first is an E1cb mechanism in which an initial
deprotonation event generates a carbanionic intermediate prior to expulsion of the leaving group.
Synthesis of Allylic Alcohols from Oxazolinyloxiranes
isomerization of the studied oxiranes. ... 3

Alternative routes planned to make the BH reaction reasonably fast use
the “MAC” procedure (Michael addition−aldol reaction−Cope elimination). ... Allylic alcohols 6a−e are likely the
result of a β-elimination reaction involving the methyl group and the oxygen of the oxirane ring, the α-elimination ...
Solvolytic Enolization of Scytalone
derivatives involving the intermediacy of ketenes is well documented. ... 17 Because the presence of electron-withdrawing groups is known to substantially facilitate
elimination reactions, some carboxylic acid derivatives possessing relatively poor leaving groups can also generate ketenes with the elimination mechanism ranging from
E2 to E1cB ... 18
Consequently, aminolysis of activated esters including acetoacetyl and malonyl
coenzyme A derivatives proceed through a E1cB mechanism.
Influence of steric effects upon the rate constants for competing BAC2 and E1cB ester
hydrolyses
hydrolyses ...
Associative and Dissociative Pathways in the Alkaline Hydrolysis of Aryl 2-
Hydroxycinnamates
The alkaline hydrolysis of title esters possessing acidic leaving groups follows an E1cB mechanism
involving the participation of an extra extended p-oxo ketene intermediate. ... Reactivity
comparison, Arrhenius parameters, and trapping of the above-depicted unsaturated intermediate
strongly suggest that the alkaline hydrolysis of the title ester follows a mechanism of the E1cB
type. ... To gain knowledge on the role played by the nature of the bridge interposed between
hydroxyl and carbonyl groups in esters of the title type, in principle able to hydrolyze through
dissociative pathways via the conjugate base of the substrate (E1cB ... ...
Acylation through Ketene Intermediates
derivatives involving the intermediacy of ketenes is well documented. ... 17 Because the presence of electron-withdrawing groups is known to substantially facilitate
elimination reactions, some carboxylic acid derivatives possessing relatively poor leaving groups can also generate ketenes with the elimination mechanism ranging from
E2 to E1cB ... 18
Consequently, aminolysis of activated esters including acetoacetyl and malonyl
coenzyme A derivatives proceed through a E1cB mechanism
Claisen Condensation as a Facile Route to an α-Alkoxy-cinnamate:

Synthesis of Ethyl (2S)-2-Ethoxy-3-(4-hydroxyphenyl)propanoate
The synthesis involves a Claisen-type condensation in which the elimination was unexpectedly
promoted by an excess of the ester. ... The type of elimination (E1, E2, or E1cB) by which the
reaction takes place has not been determined since such an investigation was beyond the scope of
this work.
Biomimetic Transannular Oxa-Conjugate Addition Approach to the 2,6-
Disubstituted Dihydropyran of Laulimalide Yields an Unprecedented
Transannular Oxetane
We demonstrated that under acid-catalyzed conditions the model substrate undergoes

elimination, generating a postulated activated triene, followed by oxa-conjugate addition. ...
This is in direct contrast to the electronic arguments in favor of 1,4- or E1cB elimination, where
the π orbital of the oxetane enol/enolate is energetically and geometrically aligned to interact
with the ether σ* orbital. ... Base-mediated E1cB elimination followed by oxa-conjugate addition
seemed a viable route to generating the desired dihydropyrans.
Removal of Acyl Protective Groups from Glycopeptides: Base Does Not

Epimerize Peptide Stereocenters, and β-Elimination Is Slow
Removal of Acyl Protective Groups from Glycopeptides: Base Does Not Epimerize Peptide
Stereocenters, and β-Elimination Is Slow ... O-Linked glycosides of serine and threonine have
been suggested to undergo E1cB elimination in aqueous sodium hydroxide with an amino acid
enolate ion as an intermediate.
Large, inverse solvent isotope effects: a simple test for the E1cB mechanism ... Catalysis of the β-
Elimination of HF from Isomeric 2-Fluoroethylpyridines and 1-Methyl-2-fluoroethylpyridinium
Salts. ...
One-Pot Reactions of N-(Mesyloxy)phthalimides with Secondary Amines

to 2-Ureidobenzamides, 2-Ureidobenzoic Acids, Ethyl 2-
Ureidobenzoates, or Isatoic Anhydrides
The key step of the sequence involves addition and elimination of an enolic lactam in a single
step and 70% yield, employing an organocuprate reagent. ... The elimination of the acetate group
of compound 7 leading to E-Boc-pulchellalactam 8 with high E selectivity proceeded presumably
via the E1cB mechanism42-46 with the help of a steric factor from the N-Boc moiety. ... We assume
that allylic deprotonation of compound 4 and condensation with aldehyde led to Z-
pulchellalactam 1 also through an E1cB mechanism42-46 via tert-butoxycarbonyl group (Boc)
migration (Scheme 3). ...
Diastereoselective Synthesis of Diketopiperazine Bis-α,β-epoxides
13, 15) As a means to introduce desired substituents at the 3 and 6 positions of the 2,5-
diketopiperazines, a majority of synthetic studies have been devoted to the
elimination−nucleophilic attack of compounds A in the presence of nucleophiles, often under
acidic conditions, to form B (Scheme 1a). ... (26) One plausible explanation for the cis selectivity
is an E1cb pathway through the transition state 8β. ...
NaOH-Catalyzed Thiolysis of α,β-Epoxyketones in Water. A Key Step in
the Synthesis of Target Molecules Starting from α,β-Unsaturated
Ketones
Elimination Reactions of (E)- and (Z)-Benzaldehyde O-Benzoyloximes. ... In addition, an E1cb

mechanism is negated by the substantial values of kH/kD and |β1g|.6-8 A similar mechanism has been
proposed for the nitrile-forming eliminations from benzaldoxime derivatives under various
conditions
3-Deoxy-3,3-difluoro-D-arabinofuranose: First Stereoselective

Synthesis and Application in Preparation of gem-Difluorinated Sugar
Nucleosides
benzoylcytosine failed to give our desired protected nucleosides 27‘, but the regioisomer 27 was obtained in 47% yield (two steps) along with β-elimination product 28 in
22% yield (two steps). ... 32

Depending on the structures of the starting sulfoxides, both E1cb and E2
pathways are known to give the α-thiocarbocation intermediates. ...
Diethylzinc-Mediated One-Step Stereoselective Synthesis of α-
Fluoroacrylates from Aldehydes and Ketones. Two Different Pathways
Depending on the Carbonyl Partner
Aldolate A is prone to E2 elimination due to antiperiplanar arrangement of bromine atom and

leaving group and as a consequence direct attack by diethylzinc affords fluoroacrylate (Z)-1. ...
Moreover, two different pathways have been identified, depending on the involved carbonyl
partner (E2-type mechanism for aldehydes and E1cb in the case of ketones
Elimination Reactions of (E)- and (Z)-Benzaldehyde O-Benzoyloximes.

Transition State Differences for the Syn- and Anti-Eliminations Forming
Nitriles
Elimination Reactions of (E)- and (Z)-Benzaldehyde O-Benzoyloximes. ... In addition, an E1cb

mechanism is negated by the substantial values of kH/kD and |β1g|.6-8 A similar mechanism has been
proposed for the nitrile-forming eliminations from benzaldoxime derivatives under various
conditions. ...
Elimination Reactions of (Z)-Thiophene- and (Z)-Furan-2-carbaldehyde

O-Benzoyloximes. Effect of β-Aryl Group upon the Nitrile-Forming Anti
Transition State
Elimination Reactions of (Z)-Thiophene- and (Z)-Furan-2-carbaldehyde O-Benzoyloximes. ... In

addition, an E1cb mechanism is negated by the substantial values of kH/kD and |β1g|.24,2
β-Isocupreidine-Catalyzed Asymmetric Baylis−Hillman Reaction of
Imines
Among them, there would be two betaine intermediates B and C that are stabilized through
hydrogen-bonding between the amidate ion and the phenolic OH. On taking the anti-periplanar
arrangement13 of the ammonium portion and the α-hydrogen of the ester group in the subsequent
E2 or E1cb reaction (see Newman projection D), intermediate C suffers from more severe steric
interaction than intermediate B as depicted in Scheme 4. Thus, the difference in the reaction rate
of the elimination step of B and C would result in (S)-enriched enantioselectivity through
equilibration
Isocyanides and Arylacetic Acids: Synthesis and Reactivity of 3-Aryl-2-

acyloxyacrylamides, an Example of Serendipity-Oriented Synthesis
In principle, other mechanisms could not be ruled out, for example, the direct formation of a
ketene from a with a E1cb elimination and its subsequent reaction with a molecule of acid and
one of isocyanide, in a way similar to that reported by Ugi, although the absence of a base
catalysis makes this hypothesis less likely. ...
Multicomponent Reaction Discovery: Three-Component Synthesis of
Spirooxindoles
The product of E1CB elimination of 27 (an isatylidene) cannot be ruled out as a reaction
intermediate. ...
Cooperative, Highly Enantioselective Phosphinothiourea Catalysis of

Imine−Allene [3 + 2] Cycloadditions
The role of Et3N is most likely to promote elimination and liberation of the phosphine catalyst via
either E2 or E1cb mechanisms. ...
Structural Revision of Stemoburkilline from an E-Alkene to a Z-Alkene
e had speculated that 2 arose from 1 via a ring-opening reaction involving an elimination process.
... The stereochemical outcome of the base/TMSCl-initiated ring-opening reaction of 1 and 3 can
be rationalized as occurring through an E1cB mechanism, as shown in Scheme 3.
One-Pot Organocatalytic Domino Michael-Aldol and Intramolecular S N2
Reactions. Asymmetric Synthesis of Highly Functionalized
Epoxycyclohexanone Derivatives
The organocatalytic reaction is based on the full stereochemical control of first a Michael
reaction, followed by an aldol reaction, and finally, depending on the product of choice, a S N2 or
an E1cB reaction. ... Scheme 4. One-Pot Domino Organocatalytic Michael-Aldol and Elimination
Reactiona
Improved Methodologies for the Preparation of Highly Substituted

Pyridines
-9
One of the most popular versions of this reaction utilizes enamines 2 as dienophiles in an
inverse-electron-demand Diels−Alder reaction, followed by in situ loss of nitrogen from 3 and
subsequent elimination/aromatization (Scheme 1). ... This could allow, for instance, either an E1cb mechanism (if the anion was
sufficiently stable) or epimerization of this carbon center, leading to an anti-arrangement of proton and adjacent leaving group and hence a facile E2 elimination. ...
Thus, zwitterion 4‘ could facilitate elimination to the corresponding pyridine (by allowing an E1cb mechanism or epimerizing adjacent to the amine leaving group).
A Carbohydrate Approach to the Enantioselective Synthesis of 1,3-

Polyols
Treatment of per-O-benzoyl-D-glycero-D-gulo-heptono-1,4-lactone (2) with tertiary amines
afforded selectively and with good yields the (5H)-furan-2-one derivatives 3, 4, and 5, formed by
controlled elimination of one, two, or three molecules of benzoic acid, respectively. ... We have
proposed15 an E1cB ... The introduction of an endocyclic double bond favors the abstraction of H-
5, being the resulting carbanion stabilized by conjugation with an α,β-unsaturated carbonyl group,
and also an E1cB mechanism would operate during the second elimination, which leads to 4. ...
An Unusual Michael Addition of 3,3-Dimethoxypropanenitrile to 2-Aryl

Acrylates: A Convenient Route to 4-Unsubstituted 5,6-
Dihydropyrido[2,3-d]pyrimidines
The E1cB mechanism in the alkaline hydrolysis of N,N-diethyl-P-(3,5-dimethyl-4-

hydroxyphenyl)phosphonamidic chloride

Selective Inhibition of Type II Dehydroquinases

The elimination has been shown to proceed by an E1CB mechanism, probably via an enolate
intermediate 3,12 and involves loss of the more acidic 2-pro-S hydrogen of the substrate, in an anti
elimination of water (Scheme 1). ... DHQase catalyzes the elimination of a water molecule from ...
Chichibabin Indolizine Synthesis Revisited: Synthesis of Indolizinones

by Solvolysis of 4-Alkoxycarbonyl-3-oxotetrahydroquinolizinium Ylides †
derivative with bromoacetone
followed by base treatment (eq 1).2 Later, the reaction was successfully expanded to the 1-(alkoxycarbonyl)methyl-2-methylpyridinium system leading to 2,3-dihydro-2-
indolizinones.5 A mechanism proposed for the reaction was that by the base-treatment of the pyridinium salts, the corresponding ylide was formed as an reactive
intermediate and indolizines were produced via an intramolecular nucleophilic attack of the active methylene to the carbonyl group followed by elimination of water (or
alcohol). ... For alcoholysis (R ≠ H), cyclization to indolizinone F proceeds through ketene intermediate E, which is formed from C by the elimination of R1 presumably via
the E1cB mechanism. ... 8

Furthermore, the formation of hydrolyzed betaine 19 in both reactions, though in
low yield, was only explained by the ketene intermediate via the E1cB mechanism because no
hydrolysis was observed with tert-butyl ester 17c in water.
Reduction of the Pesticides Oxamyl and Methomyl by FeII: Effect of pH and Inorganic
Ligands
An FeII-independent, oxygen-independent elimination reaction (E1cb mechanism) results in the

formation of an oxime product, methylamine and CO2. ... The larger value of kOH− for oxamyl
(relative to methomyl) is due, in part, to greater acidity at the N-methyl carbamate amide
nitrogen; the conjugate base of the amide group is the reactive species for E1cb elimination (29).
... Therefore, we ascribe methomyl degradation to an acid-catalyzed hydrolysis reaction (mech
anism unclear) rather than to E1cb elimination.
Chiral Photocages Based on Phthalimide Photochemistry

A new class of photoremovable protecting groups, based on a photoinduced decarboxylation
reaction coupled with the elimination of the caged molecule, is described for 2-phthalimido-3-
hydroxy-propionate derivatives. ... This carbanion can be protonated by the aqueous solvent or
eliminate acetate via E1cB mechanism, yielding either the cis or the trans double bond. ...
Sulfonyl-Containing Aldophosphamide Analogues as Novel Anticancer

Prodrugs Targeted against Cyclophosphamide-Resistant Tumor Cell
Lines
A series of sulfonyl-group containing analogues of aldophosphamide (Aldo) were synthesized as

potential anticancer prodrugs that liberate the cytotoxic phosphoramide mustards (PM, IPM, and
tetrakis-PM) via β-elimination, a nonenzymatic activation mechanism. ... Elimination of
phenoxide from β-substituted ethyl phenyl ethers: Evidence for E1cB mechanism
Computer-Aided Reaction Design. Development of a New Facile

Procedure to Synthesize 2-Mercapto-3-alkoxycarboxylate on the Basis
of ab Initio Molecular Orbital Calculations
It was confirmed that the substrate with an ester fragment prefers the E1cB to the SN2
mechanism. ... That is, β-elimination mainly proceeds to form 5 when 1a was used as the
substrate.
Novel Type Elimination Reactions of Sulfoxides Bearing Several

Heteroaromatics: Trapping of Sulfines with 2,3-Dimethyl-1,3-
butadiene
Novel Type Elimination Reactions of Sulfoxides Bearing Several Heteroaromatics: Trapping of

Sulfines with 2,3-Dimethyl-1,3-butadiene ... Therefore, in the case of 4a, the rate-determining
step is not the α-methylene hydrogen abstraction step but the elimination step of the 4-methyl-
1,2,4-triazolyl group; this means that the possible mechanism for 4a will be via an E1cB or an
E1cB-like transition state and, consequently, the possibility of existing as enol transition state
1a5a−4a5a will be increased, stabilized by hydrogen bonding between the hydroxy and sulfinyl
groups, successively, to form (Z)-sulfine predominantly. ... In the case of 3a in the presence of an
external base (entries 7−9), the trans-selectivity became very low compared with that in the
absence of base, suggesting that the elimination mechanism shifts to an E1cB-like or E1cB
mechanism which will raise the possibility of cis-selectivitiy. ...
Structure and Reactivity of trans-Bis[2-(2-

chloroethyl)pyridine]palladium Chloride (1). A Study on the
Elimination Reaction of 1 and 2-(2-Chloroethyl)pyridine Induced by
Quinuclidine in Acetonitrile
A Study on the Elimination Reaction of 1 and 2-(2-Chloroethyl)pyridine Induced by Quinuclidine in

Acetonitrile ... It should be considered that the mechanism of the elimination reaction from 1 can
be E2 concerted or E1cb ... In previous studies,1,2,5,7 it was shown that systems where the pyridine
ring is protonated or interacts with a metal ion react by the E1cb mechanism. ...
New Horner−Wadsworth−Emmons Type Coupling Reaction between Nonstabilized β-

Hydroxy Phosphonates and Aldehydes or Ketones
Treatment of nonstabilized β-hydroxy phosphonic acid mono methyl esters with diisopropyl
carbodiimide at ambient temperature leads to clean stereospecific elimination. ... In the
Wadsworth−Emmons reaction,6 the reversible formation of the pentavalent phosphorus species 15
is thought to precede collapse to the stabilized anion 16, and E1cb elimination leads to release of
phosphate and the coupled enone product 17 (Scheme 3).
6) Cycloaddition Chemistry of 1,3-Thiazolium-4-olate Systems. †

Reaction with Nitroalkenes and Interpretation of Results Using PM3
Calculations
The elimination
pathway is not consistent with the E2 mechanism owing to stereoelectronic effects. ... It is known
that the E1cB mechanism would most likely be found with substrates containing acidic protons
and poor leaving groups
Catalytic Mechanism of SHCHC Synthase in the Menaquinone

Biosynthesis of Escherichia coli: Identification and Mutational Analysis
of the Active Site Residues
The 2,5-elimination of pyruvate from SEPHCHC by MenH can occur by simultaneous proton
abstraction and pyruvate dissociation in a concerted E2 elimination or through a dienolate
intermediate in a two-step E1cb ... The one-step elimination is not favored in view of the well-
established notion that base-induced β-eliminations involving breakage of a C−H bond at an α-
position to a carbonyl group proceed by an E1cb mechanism rather than a concerted mechanism
(54). ... In comparison to 3-flourocyclohexene, SEPHCHC has a much more acidic proton in the
elimination due to the 2-succinyl group and a poorer leaving group (pyruvyl enolate) than
fluoride, both of which strongly favor an E1cb mechanism (54-56). ...
Two-Step Potentially Prebiotic Synthesis of α-D-Cytidine-5‘-phosphate

from D-Glyceraldehyde-3-phosphate
6
Expectations that this E1cb irreversible elimination ... It was found that incubation of a D2O
solution of 4 and 5 for a day at pD = 9.4 resulted in significant elimination of phosphate from 5
even before 4 had undergone significant enolization (as evidenced by the lack of exchange of the
CH2 (and CH) protons of 4 for deuterons).
Alkyl 2,2,2-Trifluoroethanesulfonates (Tresylates):

Elimination−Addition vs Bimolecular Nucleophilic Substitution in
Reactions with Nucleophiles in Aqueous Media1
Alkyl 2,2,2-Trifluoroethanesulfonates (Tresylates): Elimination−Addition vs Bimolecular

Nucleophilic Substitution in Reactions with Nucleophiles in Aqueous Media 1 ... Kinetic and product
studies are consistent with the following: (a) the reaction of tresylates with water is the normal
sulfonic ester hydrolysis and (b) reaction with hydroxide is an (E1cB)rev process with loss of HF to
yield the alkyl 2,2-difluoroethenesulfonate, ROSO 2CH CF2, which rapidly yields the observed
products.
Desymmetrization of a meso-Allylic Acetal by Enantioselective Conjugate Elimination
Desymmetrization of a meso-Allylic Acetal by Enantioselective Conjugate Elimination ... The

sparteine, closely associated to the cation, could then either favor one of the two enantiomers
through a rapid equilibration process18 of 7Li-b or accelerate the elimination step (E1cB) for one
of those enantiomers (dynamic kinetic resolution).
New Telluride-Mediated Elimination for Novel Synthesis of 2′,3′-
Didehydro-2′,3′-dideoxynucleosides
New Telluride-Mediated Elimination for Novel Synthesis of 2′,3′-Didehydro-2′,3′-dideoxynucleosides

... Under the NaBH4 reduction, the telluride is probably reduced first by hydride, thereby
generating a carbanion at the 2′-position and followed by elimination via an E1cb mechanism
Nuclear Magnetic Resonance Studies on Covalent Modification of Amino

Acids Thiol and Amino Residues by Monofunctional Aryl 13C-
Isocyanates, Models of Skin and Respiratory Sensitizers:
Transformation of Thiocarbamates into Urea Adducts
Kinetic evidence on the hydrolysis of N-arylcarbamate thioesters through an E1cB mechanism

(unimolecular elimination via the conjugate base) and elimination of an isocyanate was reported
(39). ... This hypothesis has never been in fact definitely proved in the sense that, even if thought
that the isocyanate is newly released, the reaction with a competing nucleophile, other than
water, most probably occurs through a direct addition−elimination process on the carbonyl
chemical function of the thioester adduct (Bac2 mechanism) without real release of the
isocyanate (E1cB mechanism). ... The E1cB mechanism would first involve a base-catalyzed
deprotonation of the nitrogen, followed by elimination of a nucleophile to release the isocyanate,
which seemed not to be likely in our experiments.
Simple Approach to β-Lactam Derivatives from N-Acylimidazoles
This would be possible if carboxylic derivatives of type 5 possess a relatively weak X-CO bond that
would provide a sizable equilibrium concentration of ketene of type 2, and there is a possibility
for fast elimination of HX in the absence of basic catalysts (i.e., tertiary amines) that can produce
undesirable zwitter-ionic adducts. ... The only relevant, similar examples involve generation of ethyl ketenes from N-acylbenzotriazoles by
thermolysis17 or treatment with NaH.18 These harsh conditions are understandable, since the low basicity of imidazole is not sufficient for producing ketenes from N-
acylimidazoles through E1cb elimination reaction. ... Most probably, the lack of reactivity of alkylsulfinylacetic acids is due to the lower acidity21 of the α protons that
precludes E1cb elimination of imidazole in the corresponding N-acylimidazoles and formation of ketenes of
Total Synthesis of (+)-Epilupinine via An Intramolecular Nitrile Oxide-

Alkene Cycloaddition
We hypothesized that the instability of 9 and 10 may be caused by their intramolecular E1cB
elimination, in which the amine group may play dual roles as shown in Scheme 5 (by using 10 as a
model). ... Thus, the amide-protected(9) (as a weak base) or α,α-disubstituted(13) (without α-
protons) aldehydes were successfully prepared in literature because they could not carry out an
intramolecular E1cB elimination. ... aA retro-Micheal addition by an intramolecular E1cB
elimination ...
An Olefination via Ruthenium-Catalyzed Decarbonylative Addition of

Aldehydes to Terminal Alkyne
s
The well-known Wittig reaction provides access to C═C bonds with higher efficiency and better regio-
and stereoselectivities over the classical elimination reactions (E1, E2, E1cB). ... Finally, reductive
elimination affords the decarbonylative addition product and CO and regenerates the active ruthenium complex A
Probing the Catalytic Mechanism of S-Ribosylhomocysteinase (LuxS)
with Catalytic Intermediates and Substrate Analogues
Since [3-F]SRH reacted much faster than [3-Br]SRH, the elimination reaction must occur
through the E1cb mechanism (i.e., rate-limiting abstraction of the C2 proton to form a
carbanion intermediate first, followed by the fast release of halide ion). ... [3-F]SRH and
[3-Br]SRH, while disappointing as suicide inhibitors, provide alternative substrates to
examine the function of active-site residues during the first catalytic step, since the E1cb
elimination reaction involves initial deprotonation at the C2 position, which closely
mimics the deprotonation event in the first catalytic step. ... Substrate analogues [3-F]SRH
and [3-Br]SRH act as time-dependent inhibitors of LuxS, due to enzyme catalyzed
elimination of the halide ions via an E1cb mechanism. ...
Use of 4-Cyanocoumarins as Dienophiles in a Facile Synthesis of Highly

Substituted Dibenzopyranones
(8) In this paper, we present a simple, general, palladium-free method for the synthesis of
highly substituted dibenzopyranones using a Diels−Alder reaction between 4-
cyanocoumarins and 1-oxygenated dienes followed by elimination−aromatization with
potassium tert-butoxide. ... Further support for the E1cb mechanism was obtained from
the regioisomeric Diels−Alder adduct 17, prepared in good yield from the reaction of 3-
cyanocoumarin and the 1-silyloxybutadiene 7
Synthesis of Substituted Chromanones: An Organocatalytic Aldol/oxa-
Michael Reaction
Development of this synthetic strategy revealed an unexpected kinetic anti-Saytzeff elimination;

an origin for the observed selectivity is suggested on the basis of the results of quantum chemical
calculations. ... Through a presumed E1cB mechanism, the 16a/16b mixture was quantitatively
converted to enone phenol 26.
Room Temperature Acylketene Formation? 1,3-Dioxin-4-ones via

Silver(I) Activation of Phenylthioacetoacetate in the Presence of
Ketones
) Thermolysis of β-ketoesters 4 leads to the loss of ROH via concerted elimination. ...
Either of the resulting cationic intermediates 17 and 18, upon proton loss, would give the
zwitterion 19, which could collapse directly to acetylketene (20) [Douglas and co-workers
have shown(14) that E1cb elimination from the anion of thioacetoacetates (acetoacetyl
CoA) is facile
Conversion of Cyclic Vinyl Sulfones to Transposed Vinyl Phosphonates
Protection of the diol as the bismethyl ether was followed by oxidation of the sulfide to the
sulfone 9b and elimination of the OMe group to yield vinyl sulfone 10 in 78% overall yield (Scheme
1). ... Anion 22b is perfectly set for an E1cb elimination of potassium phenylsulfinate to afford
the desired vinyl phosphonate 21. ... This is presumably because the initially formed alpha-
sulfonyl anion suffers immediate E1cb elimination of the −OH group and gives a new vinyl sulfone.
...
Conversion of Cyclic Vinyl Sulfones to Transposed Vinyl Phosphonates
Protection of the diol as the bismethyl ether was followed by oxidation of the sulfide to the
sulfone 9b and elimination of the OMe group to yield vinyl sulfone 10 in 78% overall yield (Scheme
1). ... Anion 22b is perfectly set for an E1cb elimination of potassium phenylsulfinate to afford
the desired vinyl phosphonate 21. ... This is presumably because the initially formed alpha-
sulfonyl anion suffers immediate E1cb elimination of the −OH group and gives a new vinyl sulfone.
New Methods for Side-Chain Protection of Cysteine
The data obtained are consistent with a mechanism for conversion of S-Fmoc to S-Fm via
the expected elimination/addition reaction pathway shown in Scheme 3. ... The
mechanism for β-elimination in the fulvene system has been postulated to lie on the
borderline between E1cb ... When the mechanism is E1cb (presumably as it is for
nitrogen), the rate of reaction becomes dependent on removal of the Fmoc β-hydrogen. ...
Stereocontrolled Synthesis of (−)-Macrolactin A
When the alcohol is protected as its methyl or silyl ether, β-elimination results, thus
lowering significantly the yield of the desired adduct. ... Unfortunately, the
stereoselectivity of the elimination in this case was only 2:1, E/Z. ... We postulated that
the improvement in stereoselectivity may be attributed to the greater propensity of the
benzoyloxy group toward elimination (Ka = 6.46 × 10-5 vs acetic acid Ka = 1.76 × 10-5). ...
Mechanisms of Decomposition of Aryl N-(Methoxycarbonyl)sulfamates in Aqueous

Media
Identity and distribution of products formed during the acidic hydrolysis of compounds 1a−h are
consistent with the mechanistic pathway shown in Scheme 1 in which two competitive E1cB
reactions (kCO and kSO2) are involved. ... (7) The small values of kH2O/kD2O observed for kCO in 1.0 M
LCl are not incompatible with the elimination pathway c (eq 7
Nucleophilic Substitution of Methyl β-Chloro-(3-bromo-2,4,6-trimethyl)cinnamate
We are looking for probes for delineating the mechanism of bimolecular nucleophilic vinylic
substitution proceeding by an initial nucleophilic attack on the double bond (the
“addition−elimination” route).1 With mildly activated systems the stronger evidence for a
multistep route via an intermediate carbanion (eq 1) (i.e., A being an intermediate and not a
transition state) is the element effect (the relative rates k when X = F, Cl, Br, e.g., kBr/kCl),2 which
is not always available.
... If elimination takes place it should then

proceed via the E1cB route, which is not unlikely due to the activation of the α-CO 2Me group. ...
These features could be easily explained if addition of MeS -/H+ to the acetylene is sufficiently
rapid, thus avoiding its accumulation, and if the elimination to 4 is an irreversible E1cB. ...
A Double Decarboxylation Reaction of an Oxazolidinone and Carboxylic
Acid: Its Application to the Synthesis of a New Opioid Lead Compound
Ozonolysis of compound 4, prepared from iodide 3 by an elimination reaction, gave aldehyde

5. ... This result may suggest an E2 or E1cB elimination mechanism(13, 14) rather than a
mechanism that proceeds via a β-lactone. ... (15, 16) Therefore, the double decarboxylation
reaction would proceed by E1cB mechanism, in which a carbanion B, arising from the first
decarboxylation of compound 6 or the deprotonation in compound 8 by potassium carbonate,
might be stabilized by the phenyl ring and/or the carbonyl group in the oxazolidinone ring (Figure
1).
Formation of 9,10-Unsaturation in the Mitomycins: Facile

Fragmentation of β-Alkyl-β-aryl-α-oxo-γ-butyrolactones
Olefin 7 had been prepared previously by Martin sulfurane dehydration (70%) 7 where other
more conventional elimination techniques proved unsuccessful. ... Undoubtedly, this reaction can be
considered of the E1cB type, owing to the presence of the cyclohexanone carbonyl.
Could Ionic γ-Elimination Be Concerted: Clocking the Internal

Displacement Across a Cyclobutane Ring
Clearly, the proximity of the nucleophilic and electrophilic centers in β-elimination is the
reason for the rarity of the stepwise E1cB mechanism1,2 in such reactions. ... Starting with
a carbanionic intermediate, as in the E1cB mechanism, our results suggest that, under
appropriate conditions, the formation of bicyclobutane could occur via a concerted
γ-elimination reaction. ... In addition to being entropically favorable this must also
engender enthalpic advantage to serve as a rationalization of why concerted β-elimination
reactions are so frequently encountered while the E1cB mechanism is only seldom
observed.
Base-Mediated Reaction of the Bestmann−Ohira Reagent with

Nitroalkenes for the Regioselective Synthesis of
Phosphonylpyrazoles
These pyrazoles are formed in one pot via spontaneous elimination of the nitro group. ...
Protonation of 7 followed by base-assisted elimination of HNO2 (path a, E1cB) or
elimination of the NO2 group followed by intramolecular proton transfer (path b) would
furnish phosphonylpyrazole 5
A Theoretical Study of the Chorismate Synthase Reaction
3-5
Of the various possibilities, a concerted E2 or nonconcerted E1cb elimination involving
deprotonation at C6 would likely require a strong base. ... To investigate the E1cb
process, deprotonation at C6 was modeled using DHCCP, and the structure of the resulting
anion was optimized (Figure 2). ... Consistent with that finding, the enzyme-catalyzed
elimination of (6R)-[6-2H]-EPSP displayed a small kinetic isotope effect of 1.13, ...
Theoretical Studies of Eliminations. 6. The Regiochemistry and
Stereochemistry of the Gas-Phase Reactions of 3-Halocyclohexenes
with Fluoride. An ab Initio Study
The two modes of substitution (SN2 and SN2‘) have similar barriers, but are much less
favorable than elimination. ... In previous computational work by Nibbering and co-
workers,10 E1cb intermediates were identified in the reactions of hydroxide and fluoride
with 2-butenyl methyl ether, and it was determined that these intermediates are formed
via barrierless proton transfers
Diastereoselective Free Radical Halogenation, Azidation, and

Rearrangement of β-Silyl Barton Esters
1,2
Recently we reported on the stereoselective formation and elimination of β-
bromosilanes in Lewis acid promoted atom transfer additions to branched allylsilanes. ... This
result can be rationalized by an E1cb mechanism11 for the TBAF-induced elimination from 4d and 4e, a conclusion consistent with observations reported by
Fleming.10 We conclude that the results from all of the transformations are consistent; threo is the major product formed in every case. ... The TBAF
elimination results for substrates 6d and 6e suggest an E1cb elimination mechanism, a result that is consistent with the elimination reaction of thiopyridyls
4d and 4e
Facile Acylation of Sterically Hindered Alcohols through Ketene

Intermediates
In contrast to “regular” carboxylic acids such as 1e−h that acylate alcohols through acid−DCC
adducts of type 5,6 the presence of a strongly electron withdrawing group in the α-position to the
carboxyl can enable an elimination pathway through an E1cB mechanism to give the
corresponding ketenes of type 6 (eq 4). ... The formation of ketene intermediates through an
E1cB mechanism has been well established in reactions of hydrolysis or aminolysis of activated
esters including acetoacetyl and malonyl coenzyme A derivatives. 7 Furthermore, it has been
reported that some specific, highly stabilized ketenes can be prepared in a direct reaction from
carboxylic acids and DCC in the presence of triethylamine, although under relatively harsh
conditions
Elimination Reactions of (E)- and (Z)-Benzaldehyde O-Pivaloyloximes.

Transition-State Differences for the Syn and Anti Eliminations Forming
Nitriles
Elimination Reactions of (E)- and (Z)-Benzaldehyde O-Pivaloyloximes. ... Since the elimination reactions exhibit second-order kinetics and substantial k /k
H D
values, all but E2 and (E1cb ... 4
The (E1cb) mechanism requires the formation of a carbanionic
irr
intermediate in the rate-determining step.
Metal Ion Catalysis in the β-Elimination Reactions of N-[2-(4-

Pyridyl)ethyl]quinuclidinium and N-[2-(2-Pyridyl)ethyl]quinuclidinium
in Aqueous Solution
Soc., Perkin Trans. 2 2000, 453), PAF = 1.5 × 106 and is in agreement with an E1cb
irreversible mechanism (AxhDE* + DN) (Guthrie, R. D.; Jencks, W. P. Acc. Chem. ... This
proton activation can be accounted for by an E1cb mechanism and by the high stability of
the intermediate formed from the protonated substrate NH+ (Scheme 1). ... It was
previously16 shown that eq 2 reduces to = + , owing to the operating
(E1cb)I mechanism, and the values determined are as follows: = 2.54 × 10-6 s-1
(isomer 1) and = 8.75 × 10-7 s-1 (isomer 2), = 241 M-1 s-1 (isomer 1), and = 290
M-1 s-1 (isomer 2). ...
Regio- and Stereoselective Coupling of Heteroaryl-Substituted

Alkynes: New Insights into the Mechanism of Zirconium-Mediated
Cyclodimerization of Alkynes and a Facile Route to 3-
Methylenecyclobutenes
To account for the formation of 3-methylenecyclobutenes, an E1cb reaction pathway was

suggested. ... Although we still need to wait for further investigations to explain all the
above results, those reactions suggested an E1cb pathway for elimination of an amino
group. ... To account for the formation of 3-methylenecyclobutenes, an E1cb reaction
pathway was suggested.
Alkyl 2,2,2-Trifluoroethanesulfonates (Tresylates):

Elimination−Addition vs Bimolecular Nucleophilic Substitution in
Reactions with Nucleophiles in Aqueous Media1
Kinetic and product studies are consistent with the following: (a) the reaction of
tresylates with water is the normal sulfonic ester hydrolysis and (b) reaction with
hydroxide is an (E1cB)rev process with loss of HF to yield the alkyl 2,2
difluoroethenesulfonate, ROSO2CH CF2, which rapidly yields the observed products. ... It
would appear that the reaction of water (kw term) is exclusively the conventional solvolysis
usual with sulfonic esters, whereas the reaction of hydroxide anion is clearly consistent
with the reversible E1cB reaction shown below. ... A reversible E1cB process is specific
base catalyzed and is therefore not expected to show any acceleration with added amines,
provided they act only as bases and not as nucleophiles. ...
Novel Syn Intramolecular Pathway in Base-Catalyzed 1,2-
Elimination Reactions of β-Acetoxy Esters
The more acidic thioester substrates do not produce an increased amount of syn
stereoselectivity even though their elimination reactions are at the E1cb interface. ... The
research began by a study of the elimination of acetic acid from S-tert-butyl (2R*,3R*)-3-
acetoxy-2-2H1-butanethioate (5) using KOH in 3:1 v/v EtOH/H2O, producing S-tert-butyl (E)-
2-butenethioate (6), Figure 1.5 A previous mechanistic study of the elimination reaction of
S-tert-butyl 3-acetoxybutanethioate (7) had concluded that the reaction was either E2 or
E1cbirrev. ... 2,3,9,10 Thus, electron-withdrawing substituents and poor leaving groups that
produce transition states with more E1cb character may favor syn elimination
Nucleophilicity vs Basicity in the Reaction of Sodium tert-
Butoxide with β-Stannyl Ketones
Stereochemical results suggest that the elimination reactions proceed through an (E1cB)R
mechanism. ... All these observations provide strong evidence for an (E1cB)R mechanism
initiated by proton abstraction by the tert-butoxide ion, as represented in Scheme 2. ...
The E1cB mechanism is also supported by the effect of organotin moieties attached to C-3
and of substituents attached to C-2 on the elimination/substitution rat
The Alkaline Hydrolysis of Aryl (2E)-3-(4‘-
Hydroxyphenylazo)propenoates. A Kinetic Study
The
alkaline hydrolysis of the title esters, possessing three conjugated π units between the
internal nucleophile (the hydroxyl group) and the reaction center, follows an E1cB
mechanism involving the participation of an “extra extended” p-oxo azoketene type
intermediate. ... We have been able to demonstrate that the E1cB ... In the simplest case
we investigated, the hydrolysis of aryl 4-hydroxybenzoates, 2 the π-system was an aromatic
ring and we showed that esters having leaving groups with pKa values lower than about 6.5
hydrolyze through the E1cB mechanism with the participation of the unprecedented p-oxo
ketene intermediate 1.
Mechanism of Alkaline Hydrolysis of Some HO-π-COOAr Acyl
Derivatives
To gain
knowledge on the role played by the nature of the bridge interposed between hydroxyl and
carbonyl groups in esters of the title type, in principle able to hydrolyze through
dissociative pathways via the conjugate base of the substrate (E1cB mechanism), we have
studied the alkaline hydrolyses of 2,4-dinitrophenyl esters in which the π-system is a
biphenyl, azobenzene, benzylideneaniline, or stilbene skeleton. ... We have been
interested in the dissociative (E1cB ... We have previously found1 that the hydrolyses of
aryl 4-hydroxybenzoates in moderately to strongly alkaline aqueous solution follow the
usual associative route (BAc2) when the esters possess leaving groups having pKa higher than
about 6.5, whereas esters having leaving groups with lower pKa hydrolyze through the E1cB
mechanism with the participation of the unprecedented p-oxo ketene intermediate (1
Mechanisms of Acid−Base Catalysis of β-Elimination Reactions in
Systems Activated by a Pyridine Ring
The results of a kinetic study of acid−base catalysis and H/D exchange are consistent with
NH+, the protonated substrate, as the species that undergoes carbon deprotonation with an
E1cb mechanism. ... In previous studies2-5 of systems activated by a nitrophenyl group, the
mechanism of base-induced β-elimination reactions has been shown to be E1cb (ΑxhDH +
DN)6 with the intermediate carbanion formed with different degrees of reversibility
depending on the structure of the substrate. ... H/D exchange experiments showed the
incorporation of deuterium at the β-carbon during the elimination reaction in D2O, in
acetohydroxamate/acetohydroxamic acid buffer, at 50 °C and μ = 1 M KCl, in agreement
with a stepwise reversible mechanism, (E1cb)R(AxhDH + DN*).6 Further support for the
proposed mechanism has come from studies of the solvent kinetic isotope effect. ...
Synthesis of Tertiary Amides from Anionically Activated Aromatic

Trifluoromethyl Groups
The mechanism involves initial elimination of hydrogen fluoride by an E1cB mechanism to afford
an electrophilic quinone methide- or azafulvene-type intermediate that reacts with secondary
amines under aqueous conditions to afford the tertiary amide in good yield (up to 99%). ... The
mechanism involves initial elimination of HF (via an E1cB mechanism) to give a key electrophilic
quinone methide intermediate, which can be attacked by a range of nucleophiles, such as
hydroxide. ... This lower reactivity may be attributed to the lower acidity of the aniline 4b
compared to the phenol 4a, thus leading to a reduced rate for the initial E1cB elimination of HF.
Aliphatic amines gave good yields of the desired tertiary amides (Table 1, entries 20 and 21).
An Unprecedented Concerted Pathway in the Alkaline Hydrolysis of S-
Aryl Thioesters
Kinetic data indicate that the hydrolysis of S-2,4-dinitrophenyl 4‘-hydroxythiobenzoate in mild

alkaline solutions (pH 8−11) most likely follows a dissociative, E1cB pathway, through a p-
oxoketene intermediate, whereas at higher pH values an associative mechanism carries the
reaction flux. ... We have long been interested in the alkaline hydrolysis of active aryl esters of 4-
hydroxybenzoic acid, and we have provided convincing evidence that the reaction occurs via a
dissociative pathway, the E1cB mechanism, through a p-oxoketene intermediate.
Mechanism of Polymerization Reaction of 2,5-Bis(tetrahydrothiopheniomethyl)furan

Dichloride. Effect of Aromatic Resonance Energy on the Polymerization of
Bis(sulfonium) Salts
The reaction proceeds by the (E1cb) mechanism to afford a 2,5-dihydrofuran intermediate M, which undergoes a free radical polymerization reaction. ... 1,2
irr As the
substrate was changed from SH‘ ‘ to SH‘, the mechanism of the elimination pathway changed from
(E1cb)R to (E1cb)irr, the rate of the elimination reaction increased, and that of polymerization
process decreased. ... This result rules out all but E2, (E1cb)irr, (E1cb)R, and (E1cb ...
New, “Elongated” Oxo Ketene Intermediate in the Dissociative

Hydrolysis of 2,4-Dinitrophenyl (2E,4E)-5-(4‘-
Hydroxyphenyl)pentadienoate
Reactivity comparison, Arrhenius parameters, and trapping of the above-depicted

unsaturated intermediate strongly suggest that the alkaline hydrolysis of the title ester
follows a mechanism of the E1cB type. ... We are interested in the factors governing the
competition among different mechanisms in acyl transfer processes, in particular,
dissociative (E1cB ... We have previously found1 that the alkaline hydrolyses of aryl 4-
hydroxybenzoates having leaving groups with a pKa lower than about 6.5 do not follow the
usual associative pathway but proceed via an E1cB mechanism with the participation of an
unprecedented p-oxo ketene intermediate (1). ...
Competitive Mechanistic Pathways for Green-to-Red Photoconversion
in the Fluorescent Protein Kaede: A Computational Study
Instead, the stepwise E1 and new E1cb mechanisms are suggested to occur and may compete with
each other in the electronic ground state. ... As to the proposed E2-type β-elimination mechanism
for EosFP,(14) after many trials, the concerted E2-type transition state involving the simultaneous
Cα−N bond cleavage and deprotonation by Glu212 could not be found for Kaede (and possible for
EosFP), but the optimization all led to the E1 or E1cb (see below) pathway. ... E1cb Pathway
Occurrence of an Elongated p-Oxo Ketene Intermediate in the

Dissociative Alkaline Hydrolysis of Aryl (2E,4E)-5-(4‘-
Hydroxyphenyl)pentadienoates
The alkaline hydrolysis of title esters possessing acidic leaving groups follows an E1cB mechanism
involving the participation of an “extra extended” p-oxo ketene intermediate. ... Break in the
Brønsted plot of the apparent second-order rate constants versus the pKa of the leaving group
suggests that the reaction mechanism changes from E1cB to BAc2 for esters having pKa higher than
about 6. ... In the course of our studies on acyl transfer reactions we have at first provided
evidence that alkaline hydrolysis of aryl esters of 4-hydroxybenzoic acid occurs through either
associative (BAc2) or dissociative (E1cB, via intermediate 1) mechanisms, depending on the
basicity of the leaving group
Carboxylate-Induced Degradation of Poly(3-hydroxybutyrate)s
This communication shows that thermal degradation of poly(3-hydroxybutyrate)s (PHBs) is

induced by carboxylate groups via a newly proposed E1cB mechanism. ... This
phenomenon may be explained by the E1cB mechanism proposed in this work for the
degradation of poly(3-hydroxybutyrate)s possessing a hydrogen atom at the C2 carbon
(Scheme 2), where a crucial role is played by the carboxylate terminal groups. ... Scheme
2. E1cB Degradation Mechanism of PHBa ...
Ketene-Forming Elimination Reactions from Aryl Thienylacetates

Promoted by R2NH/R2NH2+ in 70 mol % MeCN(aq). Effect of the β-Aryl
Group
As the leaving group is made poorer (X = H, OCH3, and Cl), E2 transition state becomes more
skewed toward the proton transfer, as revealed by the increase in Brönsted β to 0.5−0.64, and the
E1cb ... The changes in the k1 and k-1/k2 values with the reactant structure variation provide
additional support for the competing E1cb mechanism. ... Extensive studies of ketene-forming
elimination reactions have revealed mechanistic diversity in the E2 and E1cb
Study on the Effect of the Structure of the Leaving Group in the E1cb Mechanism of
Base-Promoted .beta.-Elimination Reactions from N-[2-(p-
Nitrophenyl)ethyl]alkylammonium Ions
Study on the Effect of the Structure of the Leaving Group in the E1cb Mechanism of Base-
Promoted .beta.-Elimination Reactions from N-[2-(p-Nitrophenyl)ethyl]alkylammonium Ions ...
Proton-Activating Factors and Methyl-Activating Factors as a Mechanistic Test To Distinguish
between Concerted E2 and E1cb Irreversible Mechanisms ... Proton-Activating Factors and Methyl-
Activating Factors as a Mechanistic Test To Distinguish between Concerted E2 and E1cb
Irreversible Mechanisms
Study of reactions leading to sulfine formation. 5. Methoxide-catalyzed decomposition of

diarylmethyl(arylsulfonyl)methyl sulfoxides: a sulfine-forming elimination on the
E1cBrev/(E1cB)irrev borderline
5. Methoxide-catalyzed decomposition of diarylmethyl(arylsulfonyl)methyl sulfoxides: a sulfine-

forming elimination on the E1cBrev/(E1cB)irrev borderline

Aryl N-(Substituted Phenylsulfonyl)carbamates

Study of reactions leading to sulfine formation. 4. Evidence for a reversible E1cB

mechanism for base-induced elimination of N,N-diisopropyl-9-fluorenesulfinamide
4. Evidence for a reversible E1cB mechanism for base-induced elimination of N,N-diisopropyl-9-

fluorenesulfinamide ... Synthesis of Carbamates from Diethoxycarbonyl Hydrazine Derivatives by E1cB Eliminative
Cleavage of the N−N′-Bond Rather than Reduction ... Synthesis of Carbamates from Diethoxycarbonyl Hydrazine
Derivatives by E1cB Eliminative Cleavage of the N−N′-Bond Rather than Reduction ...
Equilibration of N-(2-cyanoethyl)pyridinium cations with substituted pyridines and

acrylonitrile. A change in rate-determining step in an E1cb reaction
A change in rate-determining step in an E1cb reaction ...
Top of Form
Equilibration of N-(2-cyanoethyl)pyridinium cations with substituted pyridines and
acrylonitrile. A change in rate-determining step in an E1cb reaction
A change in rate-determining step in an E1cb reaction ...
Study of reactions leading to sulfine formation. 4. Evidence for a reversible E1cB

mechanism for base-induced elimination of N,N-diisopropyl-9-fluorenesulfinamide
4. Evidence for a reversible E1cB mechanism for base-induced elimination of N,N-diisopropyl-9-

fluorenesulfinamide ... Synthesis of Carbamates from Diethoxycarbonyl Hydrazine Derivatives by
E1cB Eliminative Cleavage of the N−N′-Bond Rather than Reduction ... Synthesis of Carbamates
from Diethoxycarbonyl Hydrazine Derivatives by E1cB Eliminative Cleavage of the N−N′-Bond
Rather than Reduction ...


Aryl N-(Substituted Phenylsulfonyl)carbamates ...
Study of reactions leading to sulfine formation. 5. Methoxide-catalyzed decomposition of

diarylmethyl(arylsulfonyl)methyl sulfoxides: a sulfine-forming elimination on the
E1cBrev/(E1cB)irrev borderline
5. Methoxide-catalyzed decomposition of diarylmethyl(arylsulfonyl)methyl sulfoxides: a sulfine-

forming elimination on the E1cBrev/(E1cB)irrev borderline ...
Study on the Effect of the Structure of the Leaving Group in the E1cb Mechanism of
Base-Promoted .beta.-Elimination Reactions from N-[2-(p-
Nitrophenyl)ethyl]alkylammonium Ions
Study on the Effect of the Structure of the Leaving Group in the E1cb Mechanism of Base-
Promoted .beta.-Elimination Reactions from N-[2-(p-Nitrophenyl)ethyl]alkylammonium Ions ...
Proton-Activating Factors and Methyl-Activating Factors as a Mechanistic Test To Distinguish
between Concerted E2 and E1cb Irreversible Mechanisms ... Proton-Activating Factors and Methyl-
Activating Factors as a Mechanistic Test To Distinguish between Concerted E2 and E1cb
Irreversible Mechanisms ...
VBSCF Calculations on the Bimolecular (E2) Elimination Reaction. The Nature of the
Transition State
Valence bond state correlation diagrams (VBSCD) show that a simple proton transfer such as that
in the E1cB irreversible reaction is predicted to have a lower barrier than a synchronous
concerted (E2) reaction. ... They found that reactions of a number of 2-arylethyl and 2-cyanoethyl
derivatives gave transition states near the upper left corner of the figure, in some cases into
stepwise E1cB territory. ... (15) Figure 3 is such a diagram for an E1cB reaction with the first step
rate determining. ...
Synthesis of Carbamates from Diethoxycarbonyl Hydrazine Derivatives

by E1cB Eliminative Cleavage of the N−N′-Bond Rather than Reduction
Synthesis of Carbamates from Diethoxycarbonyl Hydrazine Derivatives by E1cB Eliminative

Cleavage of the N−N′-Bond Rather than Reduction ... When 9a was treated with Cs2CO3 in
MeCN/D2O and heated at reflux for 18 h the recovered starting material had the −NCH 2CO2Me
portion converted into −NCD2CO2Me, thus providing evidence for a E1cB mechanism for the
reaction, the slow step being the breaking of the N−N bond
Gas-Phase Base-Induced 1,4-Eliminations: Occurrence of Single-, Double-, and Triple-

Well E1cb Mechanisms
Gas-Phase Base-Induced 1,4-Eliminations: Occurrence of Single-, Double-, and Triple-Well E1cb

Mechanisms
A change in the rate-determining step in the E1cB reactions of N-[2-(4-

nitrophenyl)ethyl]pyridinium cations
A change in the rate-determining step in the E1cB reactions of N-[2-(4-

nitrophenyl)ethyl]pyridinium cations ...
hydrolysesInfluence of steric effects upon the rate constants for competing BAC2 and E1cB ester
hydrolyses
Borderline between E1cB and E2 mechanisms. Elimination of hydrogen chloride from

fluorene derivatives
Borderline between E1cB and E2 mechanisms. ... Ab Initio Molecular Dynamics Simulations of
Elimination Reactions in Water Solution: Exploring the Borderline Region between the E1cb and
E2 Reaction Mechanisms ... Ab Initio Molecular Dynamics Simulations of Elimination Reactions in
Water Solution: Exploring the Borderline Region between the E1cb and E2 Reaction
Mechanisms ...


Additions and Corrections - Elimination Reactions of N-(2-p-Nitrophenyl)ethyl) alkyl-

ammonium Ions by an E1cB MechanismAdditions and Corrections - Elimination Reactions of
N-(2-p-Nitrophenyl)ethyl) alkyl-ammonium Ions by an E1cB Mechanism ...
Reactions of Aryl Phenylacetates with Secondary Amines in MeCN. Structure−Reactivity

Relationship in the Ketene-Forming Eliminations and Concurrent E2 and E1cb
Mechanisms
Structure−Reactivity Relationship in the Ketene-Forming Eliminations and Concurrent E2 and E1cb

Mechanisms ... Finally, the ketene-forming elimination reactions from p-nitrophenyl p-
nitrophenylacetate promoted by R2NH/R2NH2+ buffers in 70 mol % MeCN(aq) have been shown to
proceed by concurrent E2 and E1cb mechanisms. ... The mechanistic changes from E2 to E1cb for
eliminations reactions of (2-arylethyl)ammonium ions 9 and 9-(2-chloro-2-propyl)fluorene 12 have
been concluded to be of this type
Elimination reactions of N-[2-(p-nitrophenyl)ethyl]alkylammonium ions by an E1cB

mechanism
Elimination reactions of N-[2-(p-nitrophenyl)ethyl]alkylammonium ions by an E1cB mechanism ...

Ab Initio Molecular Dynamics Simulations of Elimination Reactions in Water Solution: Exploring the
Borderline Region between the E1cb and E2 Reaction Mechanisms ... Ab Initio Molecular Dynamics
Simulations of Elimination Reactions in Water Solution: Exploring the Borderline Region between
the E1cb and E2 Reaction Mechanisms ...
REFERENCES:
WWW.PUB.ACS.ORG
I.L FINAR

Osmania University College of Technology

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Osmania University College of Technology

Uploaded by

Copyright:

Available Formats

OSMANIA UNIVERSITY COLLEGE OF

A SEMINAR ON E1CB ELIMINATION

Zaitsev’s Rule for Elimination

Elimination Reaction: Zaitsev’s Rule

The E1 and E1cB Reactions

The E1 and E1cB Reactions

All three elimination reactions – E1, E1cB, and

Biological Elimination Reactions

< < <

The transition states look like -

So if L is a strongly electron withdrawing group -

alkyl halide + strong base + heat = E2

alkyl halide + solvent + heat (solvolysis) = E1

alcohol + strong acid + heat = E1 (acid assisted)

Only E1 reactions have rearrangements (carbocations)

Only E2 reactions require anti-coplanar b -hydrogens

strong strong weak acidic

stepwise - concerted stepwise - carbocation

a -elim. if no b -H carbocation rearrangements

The cis and trans 1-fluoro-2-bromocyclohexane isomers follow different elimination

Evidence of a Borderline Region between E1cb and E2 Elimination Reaction Mechanisms: A

Catalysis of the β-Elimination of HF from Isomeric 2-

Ab Initio Molecular Dynamics Simulations of Elimination Reactions in

Elimination reactions of 2-X-4-NO2C6H3CH2C(O)OC6H3-2-Y-4-NO2 [X = H (1), NO2 (2)] promoted

Borderline between E1cB and E2 Mechanisms. Chlorine Isotope Effects

The Mechanism of Base-Promoted HF Elimination from 4-Fluoro-4-(4-

Change in Rate-Determining Step in an E1cB Mechanism during

Irreversible Inhibitors of Serine, Cysteine, and Threonine Proteases

Synthesis of Cyclopentitols by Ring-Closing Approaches

Syntheses of gem-Dihalocyclopropanes and Their Use in Organic

Structure-Based Design, Synthesis, and Biological Evaluation of

Novel 2,5-Hexanedione Analogues. Substituent-Induced Control of the Protein

Ketone 10a is usually quite susceptible to E elimination ... 28

Identification of 3-Hydroxykynurenine Bound to Proteins in the Human

Chiral Inversion and Hydrolysis of Thalidomide: Mechanisms and Catalysis by Bases

Kinetics and Mechanism of Hydrolysis of N-Acyloxymethyl Derivatives

Tandem Nitroaldol−Dehydration Reactions Employing the Dianion of

A Reductive Cyclization Approach to Attenol A

Synthesis and Structural Analysis of the Anilides of Glucuronic Acid and

Kinetics of Polymerization Reaction of α,α‘-Bis(tetrahydrothiophenio)-p-xylene

The Stereoselective Synthesis of 4‘-β-Thioribonucleosides via the Pummerer Reaction

A General Acid-Catalyzed Anion Breakdown Associated with an E1cB Reaction in the

Carbonion (ElcB)mechanism of ester hydrolysis. I. Hydrolysis of malonate esters

Mechanistic Borderline between E2 and E1cb ... Elimination reactions of 2-X-4-

Synthesis of an Estrogen Receptor β-Selective Radioligand: 5-

tion from 4-Fluoro-4-(4-

nitrophenyl)butan-2-one Is E1cB. ...

Synthesis of Five-, Six-, and Seven-Membered Heterocycles by Intramolecular Ring

The carbanion mechanism (ElcB) of ester hydrolysis. III. Some structure-reactivity

Mechanistic Borderline between E2 and E1cb ... Elimination reactions of 2-X-4-

Synthesis of Methylene- and Alkylidenecyclopropane Derivatives

functionalized ACP in 34% yield.

Synthesis of Enantiomerically Pure 1,2-Diamine Derivatives of 7-

Total Syntheses, Fragmentation Studies, and

Role of Y94 in Proton and Hydride Transfers Catalyzed by Thymidylate Synthase

Application of Base Cleavable Safety Catch Linkers to Solid Phase

An Unexpected Highly Stereoselective Double Aza-Baylis−Hillman

hydroxide and formation of PPA. ... 79

The Aminobarbituric Acid−Hydantoin Rearrangement

Carbanionic Reactivity of the Anomeric Center in Carbohydrates

Evolution of Enzymatic Activity in the Enolase Superfamily: Functional

The proposed mechanism amounts to a Dieckmann condensation (Claisen intramolecular

Conformational Dynamics along an Enzymatic Reaction Pathway: Thymidylate