Mcmurry Per I Cyclic

30.
Orbitals and Organic

Chemistry: Pericyclic
Reactions
Based on McMurry’s Organic Chemistry, 6th
edition
©2003 Ronald Kluger
Department of Chemistry
University of Toronto
Pericyclic Reactions – What Are?
 Involves several simultaneous bond-making breaking
process with a cyclic transition state involving
delocalized electrons
 The combination of steps is called a concerted
process where intermediates are skipped
Based on McMurry, Organic Chemistry, Chapter 2

30, 6th edition, (c) 2003
30.1 Molecular Orbitals of Conjugated
 Systems
 A conjugated diene or polyene has alternating double
and single bonds
 Bonding MOs are lower in energy than the isolated p
atomic orbitals and have the fewest nodes
 Antibonding MOs are higher in energy
 See Figure 30.1 for a diagram

1,3,5-Hexatriene
 Three double bonds and six  MOs

 Only bonding orbitals, 1, 2, and 3, are
filled in the ground state
 On irradiation with ultraviolet light an
electron is promoted from 3 to the lowest-
energy unfilled orbital (4*)
 This is the first (lowest energy) excited state
 See the diagram in Figure 30.2
30.2 Molecular Orbitals and Pericyclic
Reactions
 If the symmetries of both reactant and product
orbitals match the reaction is said to be symmetry
allowed under the Woodward-Hoffmann Rules
(these relate the electronic configuration of reactants
to the type of pericyclic reaction and its
stereochemical imperatives)
 If the symmetries of reactant and product orbitals do
not correlate, the reaction is symmetry-disallowed
and there no low energy concerted paths
 Fukui’s approach: we need to consider only the
highest occupied molecular orbital (HOMO) and the
lowest unoccupied molecular orbital (LUMO), called
the frontier orbitals
Based on McMurry, Organic Chemistry, Chapter
7
30.3 Electrocyclic Reactions
 These are pericyclic processes that
involves the cyclization of a conjugated
polyene
 One  bond is broken, the other  bonds
change position, a new σ bond is formed,
and a cyclic compound results
 Gives specific stereoisomeric outcomes
related to the stereochemistry and orbitals
of the reactants

Example: Electrocyclic Interconversions With
Octatriene

Example: Electrocyclic Interconversions with
Dimethylcyclobutene

The Signs on the Outermost Lobes
Must Match to Interact
 The lobes of like sign can be either on the same
side or on opposite sides of the molecule.
 For a bond to form, the outermost  lobes must
rotate so that favorable bonding interaction is
achieved

Disrotatory Orbital Rotation
 If two lobes of like sign are on the same side of the
molecule, the two orbitals must rotate in opposite
directions—one clockwise, and one counterclockwise
 Woodward called this a disrotatory (dis-roh-tate’-or-
ee) opening or closure

Conrotatory Orbital Rotation
 If lobes of like sign are on opposite sides of the
molecule: both orbitals must rotate in the same
direction, clockwise or counterclockwise
 Woodward called this motion conrotatory (con-roh-
tate’-or-ee)

30.4 Stereochemistry of Thermal
Electrocyclic Reactions
 Determined by the symmetry of the

polyene HOMO
 For thermal reactions, ground-state
electronic configuration is used to
identify the HOMO
 For photochemical reactions excited-
state electronic configuration is used.
Ring Closure of Conjugated Trienes
 Involves lobes of like sign on the same side of the
molecule and disrotatory ring closure

Contrast: Electrocyclic Opening to
Diene
 Conjugated dienes and conjugated trienes react with
opposite stereochemistry
 Different symmetries of the diene and triene HOMOs
 Dienes open and close by a conrotatory path
 Trienes open and close by a disrotatory path

 Polyenes with an even number of electron pairs
undergo thermal electrocyclic reactions in a
conrotatory,
 odd number of electron pairs undergo the same
reactions in a disrotatory sense.

30.5 Photochemical Electrocyclic
Reactions
 Irradiation of a polyene excites one electron from HOMO
to LUMO
 This causes the old LUMO to become the new HOMO,
with changed symmetry
 This changes the reaction stereochemistry (symmetries of
thermal and photochemical electrocylic reactions are
always opposite)

Rules for Electrocyclic Reactions



30.6 Cycloaddition Reactions
 Two unsaturated molecules add to one
another, yielding a cyclic product
 The Diels–Alder cycloaddition reaction
is a pericyclic process that takes place
between a diene (four  electrons) and
a dienophile (two  electrons) to yield a
cyclohexene product Stereospecific with
respect to substituents
Rules for Cylcoadditions - Suprafacial
Cycloadditions
 The terminal  lobes of the two reactants must have the
correct symmetry for bonding to occur
 Suprafacial cycloadditions take place when a bonding
interaction occurs between lobes on the same face of one
reactant and lobes on the same face of the other reactant

Rules for Cylcoadditions - Antarafacial
Cycloadditions
 These take place when a bonding interaction occurs
between lobes on the same face of one reactant and
lobes on opposite faces of the other reactant (not
possible unless a large ring is formed)

30.7 Stereochemistry of
Cycloadditions
 HOMO of one reactant combines with LUMO of other
 Possible in thermal [4 +2] cycloaddition

[2+2] Cylcoadditions
 Only the excited-state HOMO of one alkene and the
LUMO can combine by a suprafacial pathway in the
combination of two alkenes

Formation of Four-Membered Rings
 Photochemical [2 + 2] cycloaddition reaction occurs
smoothly

30.8 Sigmatropic Rearrangements
A s -bonded substituent atom or
group migrates across a p
electron system from one position
to another
A s bond is broken in the
reactant, the p bonds move, and
a new s bond is formed in the
product
Sigmatropic Notation
 Numbers in brackets refer to the two groups
connected by the s bond and designate the
positions in those groups to which migration
occurs
 In a [1,5] sigmatropic rearrangement of a
diene migration occurs to position 1 of the H
group (the only possibility) and to position 5
of the pentadienyl group
 In a [3,3] Claisen rearrangement migration
occurs to position 3 of the allyl group and
also to position 3 of the vinylic ether
Based on McMurry, Organic Chemistry, Chapter
62
Sigmatropic Stereospecificity:
Suprafacial and Antarafacial
 Migration of a group across the same face of the 
system is a suprafacial rearrangement
 Migration of a group from one face of the  system to
the other face is called an antarafacial rearrangement

Stereochemical Rules of Sigmatropic
Rearrangements
Electron Pairs Thermal Photochemical
Reaction Reaction
Even Number Antarafacial Suprafacial
Odd Number Suprafacial Antarafacial
H
H
H
H
ANTARA
SUPRA Based on McMurry, Organic Chemistry, Chapter
64
30.9 Some Examples of Sigmatropic
Rearrangements
 A [1,5] sigmatropic rearrangement involves three
electron pairs (two  bonds and one s bond)
 Orbital-symmetry rules predict a suprafacial reaction
 5-methylcyclopentadiene rapidly rearranges at room
temperature

Another Example of a Sigmatropic
Rearrangement
 Heating 5,5,5-trideuterio-(1,3Z)-pentadiene causes
scrambling of deuterium between positions 1 and 5

Orbital Picture of a Suprafacial [1,5] H
Shift

Cope and Claisen Rearrangements are
Sigmatropic
 Cope rearrangement of 1,5-hexadiene
 Claisen rearrangement of an allyl aryl ether

Suprafacial [3,3] Cope and Claisen
Rearrangements
 Both involve reorganization of an odd number of
electron pairs (two  bonds and one s bond)
 Both react by suprafacial pathways

30.10 A Summary of Rules for
Pericyclic Reactions

BOARD WORK

PROBLEM SET


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30.

Orbitals and Organic

Based on McMurry, Organic Chemistry, Chapter 2

Based on McMurry, Organic Chemistry, Chapter 3

 Three double bonds and six  MOs

Based on McMurry, Organic Chemistry, Chapter 10

Based on McMurry, Organic Chemistry, Chapter 12

Based on McMurry, Organic Chemistry, Chapter 13

Based on McMurry, Organic Chemistry, Chapter 14

Based on McMurry, Organic Chemistry, Chapter 15

Based on McMurry, Organic Chemistry, Chapter 16

 Determined by the symmetry of the

Based on McMurry, Organic Chemistry, Chapter 18

Based on McMurry, Organic Chemistry, Chapter 20

Based on McMurry, Organic Chemistry, Chapter 21

Based on McMurry, Organic Chemistry, Chapter 26

Based on McMurry, Organic Chemistry, Chapter 28

Based on McMurry, Organic Chemistry, Chapter 36

Based on McMurry, Organic Chemistry, Chapter 43

Based on McMurry, Organic Chemistry, Chapter 50

Based on McMurry, Organic Chemistry, Chapter 51

Based on McMurry, Organic Chemistry, Chapter 52

Based on McMurry, Organic Chemistry, Chapter 53

Based on McMurry, Organic Chemistry, Chapter 54

Based on McMurry, Organic Chemistry, Chapter 63

Based on McMurry, Organic Chemistry, Chapter 67

Based on McMurry, Organic Chemistry, Chapter 68

Based on McMurry, Organic Chemistry, Chapter 69

Based on McMurry, Organic Chemistry, Chapter 70

Based on McMurry, Organic Chemistry, Chapter 71

Based on McMurry, Organic Chemistry, Chapter 76

Based on McMurry, Organic Chemistry, Chapter 77

Based on McMurry, Organic Chemistry, Chapter 85

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