Vol. 8, No.

Chemical Ligation

Chemical Ligation by
Click Chemistry
Native Chemical Ligation
Staudinger Ligation
Diphenylphosphinemethanethiol:
efficacious reagent for traceless Organic Azides and
Staudinger ligation
Azide Sources
Functionalized Alkynes
 

Introduction Vol. 8 No. 1

More and more researchers face the task of selectively combining
large molecules, attaching molecular probes, or covalently Aldrich Chemical Co., Inc.
immobilizing substrates on surfaces. In particular when biopolymers Sigma-Aldrich Corporation
and bioconjugates are involved there is an urgent need for mild and 6000 N. Teutonia Ave.
biocompatible reaction conditions. A toolbox of several powerful Milwaukee, WI 53209, USA
chemical ligation techniques already exists and is continually being
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In this issue of ChemFiles, we provide an overview of modern To Place Orders
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Introduction

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and biology. The most prominent chemical ligation techniques
(click chemistry, native chemical ligation, and Staudinger ligation) will be discussed. A
comprehensive listing of available organic azides and functionalized alkynes rounds off this
issue of ChemFiles with valuable building blocks for click chemistry or Staudinger ligation.
If you are unable to find the specific reagent you need, “Please Bother Us.” with your
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ChemFiles (ISSN 1933–9658) is a publication of

About Our Cover Aldrich Chemical Co., Inc. Aldrich is a member of the
The cover structure depicts diphenylphosphinemethanethiol, the most efficacious Sigma-Aldrich Group. © 2008 Sigma-Aldrich Co.
reagent known today to induce traceless Staudinger ligations (Raines ligation reagent).
Diphenylphosphinemethanethiol can be obtained easily from the shelf-stable precursor
670359 by removing the acetyl and borane protective groups.

Chemical Ligation by Click Chemistry—A “Click” Away from Discovery
The traditional process of drug discovery based on natural
secondary metabolites has often been slow, costly, and labor-
intensive. Even with the advent of combinatorial chemistry
and high-throughput screening in the past two decades, the
generation of leads is dependent on the reliability of the individual
reactions to construct the new molecular framework.
Click chemistry is a newer approach to the synthesis of drug-
like molecules that can accelerate the drug discovery process
by utilizing a few practical and reliable reactions. Sharpless and
co-workers have defined what makes a click reaction: one that
is wide in scope and easy to perform, uses only readily available
reagents, and is insensitive to oxygen and water. In fact, water is
in several instances the ideal reaction solvent, providing the best
yields and highest rates. Reaction work-up and purification uses
benign solvents and avoids chromatography.1
Of the reactions comprising the click universe, the “perfect”
example is the Huisgen 1,3-dipolar cycloaddition of alkynes to
azides to form 1,4-disubsituted-1,2,3-triazoles (Scheme 1). The
copper(I)-catalyzed reaction is mild and very efficient, requiring no
protecting groups and no purification in many cases.2 The azide
and alkyne functional groups are largely inert towards biological
molecules and aqueous environments, which allows the use of
the Huisgen 1,3-dipolar cycloaddition in target guided synthesis3
and activity-based protein profiling,4 or the ligation of biopolymers
to probes or surfaces.5 For example, Carell and co-workers
demonstrated the labelling of alkyne modified DNA oligomers
with fluorescence probes by click chemistry.6
The triazole has similarities to the ubiquitous amide moiety found
in nature. Thus triazole formation was used for the otherwise
difficult macrocyclization of a cyclic tetrapeptide analog to a
potent tyrosinase inhibitor.7
Additionally triazoles are nearly impossible to oxidize or reduce.
This is a main reason why material science has discovered Huisgen
cycloadditions as major ligation tools in diverse areas such as
polymer science or nanoelectronics.8
Using Cu(II) salts with ascorbate has been the method of
choice for the preparative synthesis of 1,2,3-triazoles, but it is
problematic in bioconjugation applications. However,
tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine, TBTA (Figure 1),
has been shown to effectively enhance the copper-catalyzed
cycloaddition without damaging biological scaffolds.9
R2 1 mol% CuSO4
N N N N 2
5 mol% sodium ascorbate N N R
R1 H2O/tBuOH 2:1 1
R R
rt, 8 h
Scheme 1
N N
N
N
N N
N N
N H
N N
Figure 1
Ready to scale up? For competitive quotes on larger quantities or custom synthesis,
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In an extensive study Finn and co-workers only recently showed
that tris(2-benzimidazolylmethyl)amines (general structure in
Figure 2) are the most promising family of accelerating ligands
for the Cu catalyzed azide-alkyne cycloaddition reaction from
among more than 100 mono-, bi-, and polydentate candidates.10
Under both preparative (high concentration, low catalyst loading)
and dilute (lower substrate concentration, higher catalyst
loading) conditions, these tripodal benzimidazole derivatives give
substantial improvements in rate and yields, with convenient
by Click Chemistry
Chemical Ligation
workup to remove residual Cu and ligand.
A new reagent developed by Carolyn R. Bertozzi and co-workers
eliminates the toxicity to living cells that is usually associated with
the copper catalyzed Huisgen 1,3-dipolar cycloaddition.11 By using
a difluorinated cyclooctyne (Figure 3) instead of the usual terminal
alkyne a rapid cycloaddition reaction takes place even without
a catalyst. The ring strain and the electron-withdrawing difluoro
group activate the alkyne for copper-free click chemistry. This
method was used to attach fluorescent labels to cells with azide-
containing sialic acid in their surface glycans. Thus, it was possible
to study the dynamics of glycan trafficking in living cells over the
course of 24 hours with no indication that the reaction or the
labels perturb the process. This is an impressive example of how
copper-free click chemistry can be used as a biologically friendly
method to label and track biomolecules in living cells.
Sigma-Aldrich® proudly offers a choice of catalysts and ligands
for the Huisgen cycloaddition reaction. Later sections in this issue
present a comprehensive overview of available organic azides,
azide sources, and alkynes that may be applied in click chemistry.
If you want to learn about hot new product additions to the
click chemistry universe and other innovative areas of chemical
synthesis as soon as they become available, please check our
regularly updated product highlights at sigma-aldrich.com/
chemicalsynthesis.
References: (1) For recent reviews, see: (a) Kolb, H. C.; Sharpless, K. B. Drug Discovery
Today 2003, 8, 1128. (b) Kolb, H. C. et al. Angew. Chem. Int. Ed. 2001, 40, 2004.
(2)(a) Rostovtsev, V. V.; Green, L.G.; Fokin, V.V.; Sharpless, K.B. Angew. Chem. Int. Ed.
2002, 41, 2596. (b) Tornøe, C. W. et al. J. Org. Chem. 2002, 67, 3057. (3)(a) Manetsch,
R. et al. J. Am. Chem. Soc. 2004, 126, 12809. (b) Lewis, W.G. et al. Angew. Chem. Int.
Ed. 2002, 41, 1053. (4) Speers, A. E. J. Am. Chem. Soc. 2003, 125, 4686. (5) Wolfbeis,
O.S. Angew. Chem. Int. Ed. 2007, 46, 2980. (6) Gierlich, J.; Burley, G.A.; Gramlich,
P.M.E.; Hammond, D.M.; Carell, T. Org. Lett. 2006, 8, 3639. (7) Bock, V.D.; Perciaccente,
R.; Jansen, T.P.; Hiemstra, H.; Maarseveen, J.H. Org. Lett. 2006, 8, 919. (8) Lutz, J.-F.
Angew. Chem. Int. Ed. 2007, 46, 1018. (9) Chan, T.R. et al. Org. Lett 2004, 6, 2853.
(10) Rodionov, V. O.; Presolski, S. I.; Gardinier, S.; Lim, Y.-H.; Finn, M. G. J. Am. Chem.
Soc. 2007, 129, 12696. (11) Baskin, J.M.; Prescher, J.A.; Laughlin, S.T.; Agard, N.J.;
Chang, P.V.; Miller, I.A.; Lo, A.; Codelli, J.A.; Bertozzi, C.R. PNAS 2007, 104, 16793.
N N R
N
N
R = H or -(CH2)4CO2K
N N
N
R
Figure 2
O
R F
F
R = fluorescent dye or biotin
Figure 3
 

Click Catalysts and Ligands Chloro(penta­methyl­cyclo­penta­dienyl)(cyclo­octa­- 8

diene)ruthe­nium(II)
Copper(II) acetate, 98% C18H27ClRu CH3
H3C CH3
Cupric acetate FW 379.93 CH3
O H3C
C4H6CuO4
H3C O Cu2+
FW 181.63 2
Cl Ru

[142‑71‑2] 667234-250MG 250 mg

326755-25G 25 g 667234-1G 1 g
326755-100G 100 g
Penta­methyl­cyclo­penta­dienyl­bis(tri­phenyl­phos­phine)ruthe­-
Copper(I) bro­mide, 98% nium(II) chloride
Cuprous bro­mide CuBr Chloro(penta­methyl­cyclo­penta­dienyl)bis(tri­phenyl­phos- CH3
Chemical Ligation
by Click Chemistry

BrCu ­phine)ruthe­nium(II) H3C CH3

FW 143.45 C46H45ClP2Ru H3C Ru CH3
[7787‑70‑4] FW 796.32 Ph3P Cl PPh3

212865-50G 50 g [92361‑49‑4]

212865-250G 250 g 673293-250MG 250 mg
212865-1KG 1 kg 673293-1G 1 g

Copper(I) iodide, 98% (+)-Sodium L-ascorbate, ≥98%

Cuprous iodide CuI L(+)-Ascorbic acid sodium salt; Vitamin C sodium salt HO ONa

CuI C6H7NaO6
O O OH
FW 190.45 FW 198.11
OH
[7681‑65‑4] [134‑03‑2]
205540-50G 50 g A7631-25G 25 g
205540-250G 250 g A7631-100G 100 g
205540-1KG 1 kg A7631-500G 500 g
A7631-1KG 1 kg
Copper(II) sulfate, ≥99%
Cupric sulfate CuSO4 Tenta­Gel™ TBTA 8
CuO4S Tris[(1-benzyl-1H-1,2,3- N N
N
FW 159.61 triazol-4-yl)methyl]amine,
[7758‑98‑7] poly­mer bound N N
H
C1297-100G 100 g N N
N N N
C1297-500G 500 g O N

Copper(II) sulfate pentahydrate, ≥98.0% 696773-250MG 250 mg

Cupric sulfate pentahydrate CuSO4 • 5H2O
CuO4S · 5H2O Tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine, 97%
FW 249.69 TBTA N N
[7758‑99‑8] C30H30N10 N

98.0-102.0% (ACS specification) FW 530.63

N N
N
209198-5G 5 g N
N
N N
209198-100G 100 g
209198-250G 250 g
678937-50MG 50 mg
209198-500G 500 g
678937-500MG 500 mg
209198-2.5KG 2.5 kg

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Native Chemical Ligation
Introduction: Chemical Synthesis
of Peptides and Proteins
Despite competition by recombinant DNA techniques, the
synthetic preparation of peptides and proteins offers approaches
to protein engineering that are beyond the realm of biology and
the limitations of the genetic code. Unlike nature, purely synthetic
methods allow the design of peptides entirely from scratch and the
furnishing of protein analogs with virtually any unnatural residue.
Native chemical ligation usually relies on the location of suitable
Xaa–Cys ligation sites, spaced at intervals no greater than
about 40 residues in the target amino acid sequence. However,
Xaa–Cys sites in a protein’s polypeptide chain are often limiting:
Cys residues are rare or even absent in many proteins, or only
present in an unsuitable position. Yan and Dawson introduced an
approach that allows Xaa–Ala ligation sites, with a Cys residue
used in place of the native Ala residue. Subsequent desulfurization
of the ligation product with freshly prepared Raney nickel
produces the native target sequence.18 Recently, this methodology
has been extended by Kent and co-workers to the synthesis
of Cys-containing peptides by ligating fragments at Xaa–Ala

Native Chemical Ligation

Chemical peptide synthesis faces certain limitations though. junctions.19 Using acetamidomethyl (Acm) side chain protecting
Solution-phase synthesis methods are suitable for peptides with groups for Cys residues other than the ligation site, efficient and
a chain length of up to ten amino acids (Figure 1). Solid-phase selective desulfurization of the ligation site is feasible.
peptide synthesis (SPPS) broadens the range of accessible peptides
by dramatically enhancing speed and efficiency of the synthesis. References: (12) Dawson, P.E.; Muir, T.W.; Clark-Lewis, I.; Kent, S.B.H. Science, 1994,
266, 776. (13) Wieland, T.; Bokelmann, E.; Bauer, L.; Lang, H.U.; Lau, H. Justus Liebigs
Still the maximum chain length of the peptides prepared by SPPS Ann. Chem. 1953, 583, 129. (14) Torbeev, V.Y.; Kent, S.B.H. Angew Chem. Int. Ed. 2007,
is limited to about 50 amino acid residues. 46, 1667. (15) Cole, P.A. J. Am. Chem. Soc. 2006, 128, 4192. (16) Watzke, A. et al.
Angew. Chem. Int. Ed. 2006, 45, 1408. (17) Johnson, E.C.B.; Kent, S.B.H. J. Am. Chem.
The development of chemoselective reactions to give a native Soc. 2006, 128, 6640. (18) Yan, L.Z.; Dawson, P.E. J. Am. Chem. Soc. 2001, 123, 526.
peptide bond at the site of ligation allows the synthesis of (19) Pentelute, B.L.; Kent, S.B.H. Org. Lett. 2007, 9, 687.
proteins by joining smaller peptides synthesized previously by
SPPS. The challenge of this approach is to form an amide bond
chemoselectively in the presence of amino acid side chains
presenting free amines (Lys) and carboxylates (Glu/Asp). Ideally, no � Solution-phase peptide synthesis
protecting groups should be used and all chemical transformations Only small peptides (chain length < 10 aa)
should take place under mild conditions that are compatible with � Solid-phase peptide synthesis
biological environments. The most powerful technique of this kind Medium sized peptides (chain length < 50 aa)
is Native Chemical Ligation (NCL) that was introduced by Kent and
co-workers in 1994 (Scheme 1).12 Prior to this work, Wieland had � Native chemical ligation
observed the condensation of peptide thioesters in early, pioneering Peptides and smaller proteins (chain length < 200 aa)
investigations.13 Meanwhile, Native Chemical Ligation has enabled � Expressed protein ligation
the synthesis of many moderate-size proteins and glycoproteins, Chemically modified proteins (chain length > 500 aa)
culminating in the assembly of a 203 amino acid HIV protease
covalent dimer.14 Some innovative applications and improved � Staudinger ligation
procedures for NCL will be presented later in this chapter. Modification, immobilization, or combination of peptides
Expressed Protein Ligation (EPL) finally combines the strengths Figure 1
of molecular biology and chemical synthesis by filling the
SH
gap between chemistry and biology. A protein expressed by O O
+ peptide2
recombinant DNA techniques can be extended with synthetic 1
peptide SR H2N peptide2 peptide1 S
NH2
peptide fragments post-translationally. In recent examples, Cole
and co-workers used EPL for the C-terminal attachment of a
small phosphorylated synthetic peptide.15 Waldmann, Goody, and
SH
co-workers demonstrated the EPL synthesis of an azide-modified O
N-Ras protein and its site-specific immobilization onto a phosphine- peptide1 N peptide2
H
functionalized glass surface by means of the Staudinger ligation.16
Scheme 1

Native Chemical Ligation O OH

ONa
Native Chemical Ligation allows the combination of two HS
S
O
O HS
unprotected peptide segments by the reaction of a α-thioester
MESNa MPAA
with a cysteine-peptide (Scheme 1). The result of this reaction is Figure 2
a native amide bond at the ligation site, rendering this method
highly attractive for the synthesis of large peptides. Usually,
α-alkylthioesters are used because of their ease of preparation.
Since they are rather unreactive, the ligation reaction is catalyzed
by in situ transthioesterification with thiol additives. The most
common thiol catalysts to date have been either a mixture of
thiophenyl/benzyl mercaptan, or 2-mercaptoethanesulfonate
(MESNa). In a recent study, it was shown that MESNa is a poor
catalyst, requiring reaction times of typically 24–48 hours.
It is outperformed by far by certain aryl thiols. Using
4-mercaptophenylacetic acid (MPAA), proteins can be synthesized
much more rapidly (Figure 2). Chemical ligations are typically
complete in less than an hour and with high yields.17

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4-Mer­capto­phenyl­acetic acid, 97% Fmoc-Cys(Acm)-OH, ≥95.0% (HPLC, sum of enantiomers)

C8H8O2S OH Nα-Fmoc-S-acet­amino­methyl-L-cys­teine O O
FW 168.21 O C21H22N2O5S H3C N S OH
HS H
[39161‑84‑7] FW 414.47 HN
Fmoc
653152-1G 1 g [86060‑81‑3]
653152-5G 5 g 47603-5G 5 g

Sodium 2-mer­capto­ethane­sulfo­nate, ≥98.0% (RT) Fmoc-Cys(Acm)-Wang resin

Coenzyme M sodium salt; HS-CoM Na; O Nα-Fmoc-S-acet­amino­methyl-L-cys­teine O O

2-Mer­capto­ethane­sulfonic acid sodium salt; MESNA HS S ONa 4-benzyl­oxy­benzyl ester poly­mer-bound S N CH3

H
C2H5NaO3S2 O HN
Fmoc
FW 164.18
Native Chemical Ligation

[19767‑45‑4] 47613-1G-F 1 g

63705-10G 10 g H-Cys(Acm)-2-ClTrt resin

63705-50G 50 g
S-Acet­amido­methyl-L-cys­teine 2-chloro­trityl ester poly­mer-bound
S-Acet­amido­methyl-L-cys­teine hydrochloride, ≥99.0% (AT) 94399-1G-F 1 g
H-Cys(Acm).HCl O O
• HCl TentaGel S PHB-Cys(Acm)Fmoc
C6H12N2O3S · HCl H3C N S OH
FW 228.70
H
NH2 Nα-Fmoc-S-acet­amido­methyl-L-cys­teine 4-[poly(ethyl­enoxy)]benzyl ester
[28798‑28‑9] poly­mer-bound
00320-1G 1 g 86383-5G 5 g

Boc-Cys(Acm)-OH, ≥96.0% (T) Boc-Cys(Acm)-PAM resin

Boc-S-acet­amido­methyl-L-cys­teine O O
Boc-S-(acet­amido­methyl)-L-cys­teine bound to PAM resin
C11H20N2O5S H3C N S OH 61254-1G-F 1 g
H
FW 292.35 HN
Boc
[19746‑37‑3]
15376-5G 5 g

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Staudinger Ligation The phosphine reagent can be synthesized from aminoterephthalic

Introduction
The reaction between an azide and a phosphine forming
an aza-ylide was discovered almost a century ago by Nobel
Prize laureate Herrmann Staudinger. It has found widespread
application in chemical synthesis, but only recently its value as
a highly chemoselective ligation method for the preparation of
bioconjugates has been recognized.20 Both reactive functionalities
involved in this reaction are bioorthogonal to virtually all naturally
existing functionalities in biological systems and readily combine at
acid methyl ester by diazotization, followed by iodination and
subsequent Pd-catalyzed phosphinylation (Scheme 4).
The free acid moiety allows the easy attachment of a wide
choice of molecular probes to the phosphine reagent by standard
esterification or amidation procedures. Thus, a fluorescence label
or different detection probe can be linked to any biomolecule
that has been equipped with an azide function by the Staudinger
ligation even in living cells (Scheme 5).
The following paragraph shows how GlycoProfile™ azido sugars
can be incorporated into glycan structures in vivo, and be used to

Staudinger Ligation
room temperature tolerating an aqueous environment. These ideal attach a FLAG® phosphine probe chemically.
conditions make it possible to exploit the Staudinger ligation even
in the complex environment of living cells.
Staudinger and Meyer first reported in 1919 that azides react H3CO O H3CO O H3CO O
1) NaNO2 Pd(OAc)2 (1%)
smoothly with triaryl phosphines to form iminophosphoranes HCl/H2O Ph2PH
NH2 I PPh2
after elimination of nitrogen (Scheme 1).21 This imination reaction 2) KI, H2O Et3N, MeOH

proceeds under mild conditions, almost quantitatively, and without 57 % 69 %

noticeable formation of any side products. O OH O OH O OH
393673 650064
The resulting iminophosphorane with its highly nucleophilic Scheme 4
nitrogen atom can also be regarded as an aza-ylide (Scheme 2).
It may be intercepted with almost any kind of electrophilic target
HN
reagent. Common pathways include aqueous hydrolysis forming H3CO O target O
O
a primary amine and a phosphine(V) oxide in the so-called PPh2 N N N PPh2
Staudinger reduction. Quenching with aldehydes or ketones yields
imines, which is known as the aza-Wittig reaction. Even carbonyl
O O O O
electrophiles with low reactivity, like amides or esters, react with
iminophosphoranes, especially if the reaction can take place probe probe
Scheme 5
intramolecularly (Scheme 3).
References: (20) Köhn, M.; Breinbauer, R. Angew. Chem. Int. Ed. 2004, 43, 3106.
(21) Staudinger, H.; Meyer, J. Helv. Chim. Acta 1919, 2, 635. (22) Saxon, E.; Bertozzi, C.R.
Science 2000, 287, 2007.

P + N N N P N + N2 1-Methyl 2-iodo­tere­phthal­ate, 90%

C9H7IO4 O

FW 306.05 OCH3
Scheme 1 HO
I
O

R3P N R3P N 650064-1G 1 g

R' R' 650064-10G 10 g
Scheme 2
1-Methyl-2-amino­tere­phthal­ate, 98%
H N R1
N R1 R2 C9H9NO4 O
O
H R3 FW 195.17 OCH3
H 2O
R2 R3 [60728‑41‑8] HO
NH2
O
R
R P N 393673-5G 5 g
1
R R O 393673-25G 25 g
R3
R2 N C O R2 N
- R3PO H 2-(Diphenyl­phos­phino)tere­phthal­ic acid, 1-methyl 4-penta­-
N R 1 fluoro­phenyl­di­ester, 97%
R2 N C N R1 R2 1-Methyl-4-(penta­fluoro­phenyl)-2-(diphenyl­- O
HN R3
Scheme 3 phos­phino)-1,4-ben­zene­dicarboxy­late F OCH3
C27H16F5O4P F O
P
FW 530.38 O
Nontraceless Staudinger Ligation F
F
F

Bertozzi et al. pioneered the application of the Staudinger

reaction as a ligation method for bioconjugates. In the course of 679011-25MG 25 mg
their studies on the metabolic engineering of cell surfaces they 679011-100MG 100 mg
designed a phosphine with an ester moiety as an intramolecular 2-(Diphenyl­phos­phino)benzoic acid, 97%
electrophilic trap. After formation of the iminophosphorane from
C19H15O2P O
the newly designed phosphine reagent and an azide, the ester
FW 306.30 OH
moiety captures the aza-ylide in a fast intramolecular cyclization [17261‑28‑8]
reaction before hydrolysis with water can occur. This process P

ultimately produces a stable amide bond.22

454885-1G 1 g
454885-5G 5 g

Ready to scale up? For competitive quotes on larger quantities or custom synthesis,
contact your local Sigma-Aldrich office, or visit safcglobal.com.
 

GlycoProfile™ Azido Sugars N-Azido­acetyl­manno­s­amine, Acetyl­ated 8

The GlycoProfile™ Azido Sugar portfolio consists of three ManNaz O
RO N3
peracetylated azido sugars that may be incorporated into glycan C16H22N4O10 HN
O
structures chemically or by using existing biosynthetic pathways FW 430.37 OR OR O
of mammalian cells.23 Orthogonally to chemical and biological RO
R=* CH3
carbohydrate or peptide synthesis, the azide moiety offers an ideal
anchor to attach the modified glycan to surfaces, labels, peptides, A7605-1MG 1 mg
or proteins. Labelling even works in vivo by using an alternative A7605-5MG 5 mg
metabolic-system approach. The acetyl groups increase cell N-Azido­acetyl­galacto­s­amine, Acetyl­ated 8
permeability and allow the unnatural sugars to easily pass through
GalNaz O
the cell membrane. Carboxyesterases remove the acetyl groups once OR
C16H22N4O10 RO
R=* CH3
the monosaccharide is in the cell. Cells metabolize the azido sugars
Staudinger Ligation

O
FW 430.37 OR OR
using glycosyltransferases and express the sugars on the terminus
of a glycan chain both intracelullarly and on the cell surface, leaving HN
N3
the azido group unreacted. N-Azidoacetylmannosamine may also O

be introduced into the sialic acid biosynthesis pathway. A phosphine A7480-1MG 1 mg
probe containing a detection epitope such as the FLAG® peptide A7480-5MG 5 mg
can be selectively bound to the glycan by Staudinger Ligation,
resulting in a post-translationally modified glycoprotein that is N-Azido­acetyl­gluco­s­amine, Acetyl­ated 8
detected in vivo by using a FLAG®-specific antibody. This approach GlcNaz RO

permits the analysis of pathways that are regulated by particular C16H22N4O10 O O

OR
glycan post-translational modifications as well as the monitoring of FW 430.37 OR
RO R=* CH3
the intracellular glycosylation process itself. HN
N3
O

AcO
OAc A7355-1MG 1 mg
AcO
O
OAc A7355-5MG 5 mg
GalNAz
NH
N3
O

Metabolic
cell
labeling
OAc
AcO
O
AcO
O
NH
N3
O

O
CH3
O
Staudinger ..
FLAG
R

P
ligation

Puzzled by Glycobiology?
FLAG-Phosphine
R

OAc
AcO
O
AcO
O

The Glycobiology Analysis Manual is a must-have

O NH

NH O

reference guide for the fields of glycoproteomics and

O
FLAG
R
P

Labeled
glycoprotein glycomics. The Manual features:
Profiling O-type glycoproteins by metabolic labeling with an
azido GalNAc analog (GalNAz) followed by Staudinger ligation • Innovative products and kits Glycobiology
Analysis Manual
with a phosphine probe (FLAG-phosphine). • Updated and expanded
2nd edition

technical content
Reference: (23)(a) Saxon, E.; Bertozzi, C. R. Science 2000, 287, 2007. (b) Saxon, E.;
Bertozzi, C. R. Annu. Rev. Cell. Dev. Biol. 2001, 17, 1. (c) Bertozzi, C. R.; Kiessling, L. L. • Structural and functional
Science 2001, 291, 2357. (d) Dube, D. H.; Prescher, J. A.; Quang, C. N.; Bertozzi, C. R.
Proc. Natl. Acad. Sci 2006, 103, 4819.
reviews

Whether you are an expert

Glyco­Profile FLAG–Phos­phine conjugate 8 Q Glycan Labeling and

in carbohydrate biology and

Analysis
Q Glycoprotein Purification
Detection and

Tools for Glycop Q Chemical and Enzymatic

N-[4-Carbo­methoxy-3-(diphenyl­phos­phino)
roteomics and Glycom Deglycosylation

O ics Enzymatic Synthesis

chemistry or just getting

Q
and
Degradation

OCH3
benzoyl]-Asp-Tyr-Lys-Asp-Asp-Asp-Asp-Lys
C62H75N10O23P started in glycomics, the
P
FW 1359.29 DYKDDDK Glycobiology Analysis Manual
provides the products and methods you need to solve
your glycomics puzzle!
GPHOS1-1MG 1 mg
GPHOS1-5X1MG 5 × 1 mg Visit sigma.com/glycomanual and request your copy.

sigma-aldrich.com

TO ORDER: Contact your local Sigma-Aldrich office (see back cover),

or visit sigma-aldrich.com/chemicalsynthesis.
 

Traceless Staudinger Ligation

Although the previously described methods for Staudinger
ligations work well even in biological environments, a modification HS P
forming a native amide bond without leaving the unnatural
phosphine oxide moiety in the product would be more attractive
Figure 1
yet. In 2000, the groups of Bertozzi and Raines simultaneously
introduced alternative ligation strategies.24 Based on the same
O O
working principle as the nontraceless Staudinger Ligation the +
R1 SR' HS PPh2 R1 S PPh2
auxiliary phosphine reagent can be cleaved from the product after
the ligation is completed leaving a native amide bond. Thus, the N3 R2
total chemical synthesis of proteins and glycopeptides is enabled
overcoming the limitations of native chemical ligation (NCL) of a O O

Staudinger Ligation
R2 H 2O
Cys residue at the ligation juncture. R1 N
H - HSCH2POPh2
R1 S P+Ph2
-N 2
R
Among the suitable phosphine reagents for traceless Staudinger Scheme 6
ligations, diphenylphosphinemethanethiol (Figure 1), developed by
Raines and co-workers, exhibits the best reactivity profile and has 670359
BH3
already found widespread application. This Raines ligation reagent O
NaOMe, MeOH
BH3

is first acylated. Treatment with an azide leads to the formation of S PPh2

rt, 95%
HS PPh2
an aza-ylide. The nucleophilic nitrogen atom of the aza-ylide then DABCO ® 1) 95% TFA, 1 h
attacks the carbonyl group, cleaving the thioester. Hydrolysis of the toluene, 40 °C
2) DIPEA, rt
95%
rearranged product finally produces a native amide and liberates the 95%

auxiliary as its phosphine(V) oxide (Scheme 6).25 O NaOH, MeOH

S PPh2 HS PPh2
It’s recommended to use a freshly prepared Raines ligation reagent 94%
Scheme 7
because it has only a limited stability. In this issue of ChemFiles,
Sigma-Aldrich® proudly introduces new product 670359 as a HS
shelf-stable, convenient source for this highly useful reagent PH+
(sold under license for research and development purposes H+ H+
N N
only. U.S. Patent 6,974,884 and related patents apply). In the x 3 Cl-
Figure 2
acetylthiomethyldiphenylphosphine borane complex 670359,
the thiol and phosphine moiety are protected as acetyl ester and
borane adduct, respectively. The active Raines ligation reagent can Acetyl­thio­methyl-diphenyl­phos­phine 8
be liberated easily by treatment with DABCO® at 40 °C followed borane com­plex, ≥98.0%
by basic ester cleavage (Scheme 7). Hackenberger and co-workers C15H18BOPS
O
showed that acidic deprotection of the phosphine-borane was FW 288.15
advantageous in glycopeptide and cyclopeptide preparations.26 [446822‑71‑5] H3B P S CH3

In the latter case, a linear peptide with terminal azide and

phosphine-borane groups was synthesized by SPPS. 95% TFA was
used to deprotect the phosphine and the amino acid side chains 670359-250MG 250 mg
simultaneously in a single step. Diisopropylethylamine (DIPEA) was 670359-1G 1g
then added to trigger the peptide macrocyclization by traceless 1,4-Diaza­bicyclo[2.2.2]octane, 98%
Staudinger ligation, yielding cyclic Microcin J25 with 21 amino acids.
DABCO; TED; Tri­ethylene­di­amine
Other Staudinger ligation induced macrocyclizations have been C6H12N2 N
N

published previously by Maarseveen and co-workers, who FW 112.17

successfully used the Raines ligation reagent for the synthesis [280‑57‑9]
of a series of medium-sized lactams.27 Wong and co-workers D27802-25G 25 g
reported the synthesis of 14 different glycopeptides through the D27802-100G 100 g
traceless Staudinger Ligation.28 For this work, they also developed D27802-500G 500 g
a protease-catalyzed method to selectively introduce an N-terminal D27802-2KG 2 kg
azido group into an unprotected polypeptide, as it was needed for
1,4-Diaza­bicyclo[2.2.2]octane hydro­chloride, poly­mer-bound
the subsequent ligation reaction.
Dabco chloride resin; TED-Cl resin Cl
Most recently, Raines and co-workers introduced a water-soluble N
N
variant of their reagent carrying dimethylamino groups (Figure 2).
578282-5G 5 g
This substrate mediates the rapid ligation of equimolar substrates
578282-25G 25 g
in water. In a pilot experiment, traceless Staudinger ligation was
integrated with expressed protein ligation (EPL), revealing future Dabco 33-LV
opportunities in modern protein chemistry.29 1,4-Diaza­bicyclo[2.2.2]octane solution
N
References: (24)(a) Saxon, E.; Armstrong, C.R.; Bertozzi, C.R. Org. Lett. 2000, 2, 2141. C6H12N2 N
(b) Nilsson, B.L.; Kiessling, L.L.; Raines, R.T. Org. Lett. 2000, 2, 1939. (25) Soellner, M.B.; FW 112.17
Nilsson, B.L.; Raines, R.T. J. Am. Chem. Soc. 2006, 128, 8820. (26) Kleineweischede, [280‑57‑9]
R.; Jaradat, D.; Hackenberger, P.R. Contributions at the 8th German Peptide Symposium
2007, Heidelberg, Germany. (27) David, O.; Meester, W.J.N.; Bieräugel, H.; Schoemaker, 290734-100ML 100 mL
H.E.; Hiemstra, H.; van Maarseveen, J.H. Angew. Chem. Int. Ed. 2003, 42, 4373. (28) Liu, 290734-500ML 500 mL
L.; Hong, Y.-Y., Wong, C.-H. ChemBioChem 2006, 7, 429. (29) Tam, A.; Soellner, M.B.;
Raines, R.T. J. Am. Chem. Soc. 2007, 129, 11421.

Ready to scale up? For competitive quotes on larger quantities or custom synthesis,
contact your local Sigma-Aldrich office, or visit safcglobal.com.
 10

Organic Azides and Azide Sources Azido­tris(diethyl­amino)phos­pho­nium bro­mide

C12H30BrN6P CH3 CH3
Br
Since the preparation of the first organic azide, phenyl azide, FW 369.28 N
H3C CH3
by Peter Griess in 1864 this energy-rich and versatile class of [130888‑29‑8] N P N
compounds has enjoyed considerable interest. In more recent H3C N3 CH3
 ≥97.0% (AT)
years, completely new perspectives have emerged, notably
11556-1G 1 g
the use of organic azides for peptide synthesis, combinatorial
11556-5G 5 g
synthesis, heterocycle synthesis, and the ligation or modification of
biopolymers.30 The most prominent fields of application today are  98%
Huisgen 1,3-dipolar cycloadditions, and different variants of the 380822-1G 1 g
Staudinger ligation.
Ben­zene­sul­fonyl azide, functionalized silica gel
The azido group can also be regarded as a protecting group for
Organic Azides
and Azide Sources

O
coordinating primary amines, especially in sensitive substrates Si S N3
like complex carbohydrates or peptidonucleic acids (PNA).31 O

For example, it is stable to alkene metathesis conditions.32 590274-5G 5 g

Sigma-Aldrich® is offering a broad range of organic azides for your Ben­zene­sul­fonyl azide, poly­mer-bound
research. Additionally a wide choice of azide sources facilitates the
O
preparation of tailor-made organic azides. S N3
O
An elegant way to produce organic azides from unactivated
olefins was recently reported by Carreira and co-workers. A 572977-5G 5 g
catalyst, that is easily prepared from Co(BF4)2 · 6H2O and a Schiff
4-Carboxy­ben­zene­sulfo­nazide, 97%
base, allows hydroazidation with p-toluenesulfonyl azide (TsN3)
to yield alkyl azides. Mono-, di-, and trisubstituted olefins are 4-(Azido­sul­fonyl)benzoic acid O
S N3
C7H5N3O4S
tolerated in this reaction, and complete Markovnikov selectivity is O
FW 227.20 HO
observed (Scheme 1).33
[17202‑49‑2] O
References: (30) Bräse, S.; Gil, C.; Knepper, K.; Zimmermann, V. Angew. Chem. Int. Ed. 340138-2.5G 2.5 g
2005, 44, 5188. (31) Debaene, F.; Winssinger, N. Org. Lett. 2003, 5, 4445. (32) Kane-
mitsu, T.; Seeberger, P.H. Org. Lett. 2003, 5, 4541. (33) Waser, J.; Nambu, H.; Carreira, Cesium azide, 99.99%
E.M. J. Am. Chem. Soc. 2005, 127, 8294.
CsN3 CsN3

FW 174.93
Ph Ph
[22750‑57‑8]
t-Bu 510181-5G 5 g
N CO2K
510181-25G 25 g
OH
R''
R'' t-Bu R
R + TsN3
6 mol%
R'
Cobalt(II) tetra­fluoro­borate hexahydrate, 99%
R'
6 mol% Co(BF4)2 · 6 H2O N3 B2CoF8 · 6H2O Co(BF4)2 • 6H2O
30 mol% t-BuOOH, silane
EtOH, 23 °C, 2-24 h FW 340.63
Scheme 1 [15684‑35‑2]
399957-25G 25 g
399957-100G 100 g
Azide Sources
Diphenyl phos­phor­yl azide
4-Acet­amido­ben­zene­sul­fonyl azide, 97% DPPA; Phos­phor­ic acid diphenyl ester azide O
C12H10N3O3P O P O
p-ABSA O
S N3 N3
C8H8N4O3S O FW 275.20
O
FW 240.24 H3C N [26386‑88‑9]
H
[2158‑14‑7]
 97%
404764-5G 5 g
178756-5G 5 g
404764-25G 25 g
178756-25G 25 g
Azide exchange resin,azide on Amberlite IRA-400 178756-100G 100 g

368342-10G 10 g
 ≥90% (HPLC)
368342-50G 50 g 79627-50ML 50 mL

Azido­tri­methyl­silane, 95% Diphenyl­phos­phor­yl azide, poly­mer-bound

Tri­methyl­silyl azide CH3 DPPA poly­mer-bound; PS-DPPA O
C3H9N3Si H3C Si N3 O P O
FW 115.21 CH3 N3
[4648‑54‑8] 668168-1G 1 g
155071-10G 10 g 668168-5G 5 g
155071-50G 50 g 668168-25G 25 g

Azido­tri­methyl­tin(IV), 97% Lithium azide solution

C3H11N3Sn LiN3 LiN3
FW 207.85 FW 48.96
[1118‑03‑2] [19597‑69‑4]
349488-1G 1 g  20 wt. % in H2O
349488-5G 5 g
480525-25G 25 g
480525-100G 100 g

TO ORDER: Contact your local Sigma-Aldrich office (see back cover),

or visit sigma-aldrich.com/chemicalsynthesis.
 11

Potas­sium 2-(3,5-di-tert-butyl-2-hydroxy­benzyl­idene­amino)- α-Azido­iso­butyric acid solution

2,2-diphenyl­acetate, 95% 2-Azido-2-methyl­pro­pionic acid O
H3C
Potas­sium N-(3,5-di-tert-butyl­salicyl­idene)-2- C4H7N3O2 OH
H3C
amino-2,2-diphenyl­acetate CH3 FW 129.12 N3
H3C OK
C29H32KNO3 H3C N [2654‑97‑9]
FW 481.67 OH
O
 ~15% in heptane (T)
H3C CH3
CH3
52916-10ML-F 10 mL
52916-50ML-F 50 mL
676551-250MG 250 mg
676551-1G 1 g  ~15% in heptane (T)
59955-10ML-F 10 mL
Sodium azide

and Azide Sources

Organic Azides
N3Na NaN3 Azido­methyl phenyl sulfide, 95%
FW 65.01 Phenyl­thio­methyl azide S N3
[26628‑22‑8] C7H7N3S
 99.99+% (metals basis) FW 165.22
[77422‑70‑9]
438456-5G 5 g
244546-1G 1 g
438456-25G 25 g

 ≥99.0% (T) 6-(4-Azido-2-nitro­phenyl­amino)hexanoic acid N-hydroxy­-

71290-10G 10 g
succini­mide ester, ≥90%
71290-100G 100 g N-Succini­midyl 6-(4-azido-
O O O2N N3
71290-500G 500 g 2-nitro­ani­lino)hexa­noate N
C16H18N6O6 O
N
 ≥99% FW 390.35 O
H

13412-100G-R 100 g [64309‑05‑3]

13412-6X100G-R 6 × 100 g
A3407-50MG 50 mg
13412-250G-R 250 g
13412-1KG-R 1 kg (2S,3R,4E)-2-Azido-4-octa­decene-1,3-diol
13412-6X1KG-R 6 × 1 kg D-Sphingosine azide OH
13412-20KG-R 20 kg CH(CH2)12CH3
C18H35N3O2 HO

Tetra­butyl­ammo­nium azide FW 325.49 N3

[103348‑49‑8]
C16H36N4 H3C CH3
N N3- A0456-1MG 1 mg
FW 284.48 CH3
H3C A0456-5MG 5 mg
[993‑22‑6]
651664-5G 5 g 4-Azido­phen­acyl bro­mide
651664-25G 25 g 4’-Azido-2-bromo­aceto­phen­one; 4-Azido- O
Br
α-bromo­aceto­phen­one
Organic Azides C8H6BrN3O N3
FW 240.06
1-Azido­ada­man­tane, 97% [57018‑46‑9]
C10H15N3 N3 A6057-500MG 500 mg
FW 177.25  ≥98.0% (HPLC)
[24886‑73‑5]
11550-250MG-F 250 mg
276219-1G 1 g 11550-1G-F 1 g
276219-5G 5 g
4-Azido­phenyl iso­thio­cyanate, 97%
4-Azido­ani­line hydrochloride, 97%
C7H4N4S NCS
4-Amino­phenyl azide hydrochloride NH2
FW 176.20
• HCl
C6H6N4 · HCl [74261‑65‑7]
N3
N3
FW 170.60
359564-500MG 500 mg
[91159‑79‑4]
359556-250MG 250 mg 2,6-Bis(4-azido­benzyl­idene)-4-methyl­cyclo­hexan­one
359556-1G 1 g C21H18N6O O
FW 370.41
(4S)-4-[(1R)-2-Azido-1-(benzyl­oxy)ethyl]-2,2-dimethyl-1,3-
[5284‑79‑7]
dioxolane N3 N3
CH3
C14H19N3O3 N3
 97%
FW 277.32 283029-5G 5 g
O
O O  ≥90% (HPLC, calc. based on dry substance)
H3C CH3 14528-10G 10 g
573213-1G 1 g
4,4’-Diazido-2,2’-stil­bene­disulfonic acid disodium
[3aS-(3aα,4α,5β,7aα)]-5-Azido-7-bromo-3a,4,5,7a-tetra­- salt hydrate, 97%
hydro-2,2-dimethyl-1,3-benzo­dioxol-4-ol, 99% C14H8N6Na2O6S2 · xH2O N3
SO3– Na+
C9H12BrN3O3 Br FW 466.36 (Anh) • xH2O

FW 290.11 O CH3 SO3– Na+

N3
[171916‑75‑9] O CH3
N3
OH 363227-10G 10 g

493406-500MG 500 mg

Ready to scale up? For competitive quotes on larger quantities or custom synthesis,
contact your local Sigma-Aldrich office, or visit safcglobal.com.
 12

7-(Diethyl­amino)cou­marin-3-carbo­nyl azide, ≥95% (HPLC) O-(2-Amino­ethyl)-O′-(2-azido­ethyl)nona­ethylene glycol,

C14H14N4O3 O ≥90% (oligomer purity)
FW 286.29 N3 Azido-PEG-amine (n=10) O
H2N N3
[157673‑16‑0] H3C N O O C22H46N4O10 10

CH3
FW 526.62
[912849‑73‑1]
31755-25MG 25 mg
77787-500MG-F 500 mg
Ethi­dium bro­mide mono­azide, ≥95% (HPLC) O-(2-Amino­ethyl)-O′-(2-azido­ethyl)penta­ethylene glycol,
3-Amino-8-azido-5-ethyl-6-phenyl­phenan­thridi­nium bro­mide; Ethi­dium ≥90% (oligomer purity)
mono­azide bro­mide
Azido-PEG-amine (n=6) O
C21H18BrN5 H2N N3
C14H30N4O6 6
FW 420.31
Organic Azides
and Azide Sources

FW 350.41
[58880‑05‑0]
76172-500MG-F 500 mg
E2028-5MG 5 mg
O-(2-Azido­ethyl)-O-[2-(di­glycolyl-amino)ethyl]hepta­ethylene
Ethyl azido­acetate solution
glycol, ≥90% (oligomer purity)
C4H7N3O2 O
Azido-PEG-acid (n=8) O
FW 129.12 N3
O CH3 HO O
C22H42N4O12 N
[637‑81‑0] 8 N3
FW 554.59 HO
O
 ~30% in methylene chloride (NMR) [846549‑37‑9]
88539-50ML-F 50 mL 71613-500MG-F 500 mg

 ~25% in toluene (NMR) 11-Azido-3,6,9-tri­oxa­un­deca­n-1-amine, ≥90% (GC)

77213-25ML-F 25 mL
1-Amino-11-azido-3,6,9-tri­oxa­undec­ane; O-(2-Aminoethyl)-O’-(2-
 ~25% in ethanol (NMR) azidoethyl)diethyl­ene glycol; 2-{2-[2-(2-
O O
93528-25ML-F 25 mL
Azidoethoxy)ethoxy]ethoxy}ethylamine H2 N O N3
C8H18N4O3
4-Methoxy­benzyl­oxy­carbo­nyl azide, 95% FW 218.25
4-Methoxy­benzyl azido­formate O [134179‑38‑7]
C9H9N3O3 O N3 17758-1ML 1 mL
FW 207.19 H3CO
17758-5ML 5 mL
[25474‑85‑5]
152854-5G 5 g Azido Carbohydrates
152854-25G 25 g
2-Acet­amido-2-deoxy-β-D-gluco­pyran­osyl azide 3,4,6- 8
Photo­bio­tin acetate
tri­acetate, ≥98.0% (HPLC)
Bio­tin {3-[3-(4-azido-2-nitro­ani­lino)-N-methyl­pro­pyl­amino]pro­pyl­
2-Acet­amido-3,4,6-tri-O-acetyl-2-deoxy-β-D- RO
amide} acetate; N-(4-Azido-2-nitro­phenyl)-N’-(3-bio­tin­yl­amino­pro­pyl)- O
N3
O
gluco­pyran­osyl azide
N’-methyl-1,3-propane­di­amine acetate OR
R=*
[6205‑69‑2] CH3
C23H35N9O4S · C2H4O2 O RO
O HN CH3
FW 593.70 HO CH3
[96087‑38‑6] HN NH O
O2 N CH3 H H
H H
N N N 671118-250MG 250 mg
S 671118-1G 1 g
O
 ≥95% (HPLC) N3
2-Acet­amido-3,4,6-tri-O-benzyl-2-deoxy-β-D- 8
79728-1MG 1 mg
gluco­pyran­osyl azide, ≥98.0% (HPLC)
 ≥98.0% (TLC) C29H32N4O5 RO
N3
56385-1MG-F 1 mg FW 516.59 O
OR R=*
[214467‑60‑4]
Ro 15-4513 RO
HN CH3
Ethyl 8-azido-6-dihydro-5-methyl-6-oxo- O
N O
4H-imidazo[1,5-a][1,4]benzo­diazepin­e- O CH3
3-carboxy­late N 671215-100MG 100 mg
C15H14N6O3 N 8-Azido­adeno­sine 3′:5′-cyclic mono­phos­phate, ~95%
N3
FW 326.31 O
CH3
[91917‑65‑6] C10H11N8O6P NH2
FW 370.22 N N
R109-25MG 25 mg N3
[31966‑52‑6] O N N
R109-100MG 100 mg
O
O P

PEG Azides OH O OH

A1262-5MG 5 mg
O-(2-Amino­ethyl)-O′-(2-azido­ethyl)hepta­ethylene glycol,
8-Azido-cyclic adeno­sine di­phos­phate-ribo­se, ≥95% (HPLC)
≥90% (oligomer purity)
Cyclic adeno­sine di­phos­phate-ribo­se 8-azide OH OH
NH
Azido-PEG-amine (n=8) O
H2N N3 C15H20N8O13P2 N
C18H38N4O8 8 O N
FW 582.31 N3
FW 438.52 O O N N
[150424‑94‑5]
[857891‑82‑8] HO P O P O
OH O O
76318-500MG-F 500 mg
OH OH

A6830-.1MG 0.1 mg

TO ORDER: Contact your local Sigma-Aldrich office (see back cover),

or visit sigma-aldrich.com/chemicalsynthesis.
 13

1-Azido-1-deoxy-β-D-galacto­pyrano­side, 97% 3′-Azido-2′,3′-dideoxy­uridine, ≥98% (TLC)

C6H11N3O5 HO C9H11N5O4 O
FW 205.17 HO O
N3 FW 253.21 HN
[35899‑89‑9] OH [84472‑85‑5] HO O N
OH O
N3
513989-500MG 500 mg
A4810-10MG 10 mg
1-Azido-1-deoxy-β-D-galacto­pyrano­side tetra­acetate, 97%
C14H19N3O9 RO N-Azido­acetyl­galacto­s­amine, Acetyl­ated 8
FW 373.32 RO O
N3 O GalNaz OR
O
OR
[13992‑26‑2] R= * CH3 C16H22N4O10 RO
R=* CH3
O
OR FW 430.37 OR OR

and Azide Sources

Organic Azides
513970-1G 1 g
HN
N3
1-Azido-1-deoxy-β-D-gluco­pyrano­side O

C6H11N3O5 HO A7480-1MG 1 mg

FW 205.17 O
N3 A7480-5MG 5 mg
OH
[20379‑59‑3]
HO N-Azido­acetyl­gluco­s­amine, Acetyl­ated 8
OH
GlcNaz RO
514004-500MG 500 mg
C16H22N4O10 O O
OR OR
1-Azido-1-deoxy-β-D-gluco­pyrano­side tetra­acetate FW 430.37
RO R=* CH3
HN
C14H19N3O9 RO N3
N3
FW 373.32 RO O O O
OR
[13992‑25‑1] R= * CH3 A7355-1MG 1 mg
OR A7355-5MG 5 mg
513997-1G 1 g
N-Azido­acetyl­manno­s­amine, Acetyl­ated 8
1-Azido-1-deoxy-β-D-lacto­pyrano­side, 97% ManNaz O
RO N3
C12H21N3O10 HO C16H22N4O10 HN
N3 FW 430.37 O
FW 367.31 O OR OR O
HO OH
[69266‑16‑6] RO
HO O R=* CH3
O
OH OH
A7605-1MG 1 mg
OH A7605-5MG 5 mg

514012-500MG 500 mg 1-O-tert-Butyl­dimethyl­silyl 2-azido-2-deoxy-β-D-

3′-Azido-3′-deoxy­thymi­dine gluco­pyrano­side 3,4,6-tri­acetate, 97%
AZT; Azido­thymi­dine C18H31N3O8Si H3C O
O
C10H13N5O4 CH3 FW 445.54 O CH3 CH3
HN O
FW 267.24 [99049‑65‑7] O
O Si CH3
HO O N H3C O CH3 CH3
[30516‑87‑1] O H3C O
N3
N3 O
 ≥98% (HPLC) 510947-1G 1 g
A2169-25MG 25 mg
A2169-100MG 100 mg α-D-Manno­pyran­osyl azide, ≥90% (TLC)
A2169-250MG 250 mg C6H11N3O5 HO
A2169-1G 1 g FW 205.17 O
OH HO
 ≥99.0% (HPLC) HO N3
11546-100MG 100 mg
11546-500MG 500 mg M6691-100MG 100 mg

2′-Azido-2′-deoxy­uridine, ≥98.0% (N) α-D-Manno­pyran­osyl azide tetra­acetate, ≥90% (TLC)

C9H11N5O5 O 2,3,4,6-Tetra-O-acetyl-α-D-manno­pyran­osyl azide RO

FW 269.21 HN
C14H19N3O9 O O

[26929‑65‑7] FW 373.32 OR RO
R= * CH3
HO O N RO N3
O
G4168-100MG 100 mg
OH N3

11544-5MG 5 mg 2,3,4-Tri-O-acetyl-β-D-xylo­pyran­osyl azide, 8

≥98.0% (HPLC)
3-Azido-2,3-dideoxy-1-O-(tert-butyl­dimethyl­silyl)- C11H15N3O7 O
β-D-ara­bino-hexo­pyran­ose, 98% FW 301.25 H3C
O
N3
O
C12H25N3O4Si HO CH3 [53784‑33‑1] H3C O
CH3
FW 303.43 O CH3
O Si CH3 O
O
[189454‑43‑1] N3 CH3 CH3 O

OH 670790-1G 1 g
497029-250MG 250 mg 670790-5G 5 g

Ready to scale up? For competitive quotes on larger quantities or custom synthesis,
contact your local Sigma-Aldrich office, or visit safcglobal.com.
 14

Functionalized Alkynes [(1,1-Dimethyl-2-pro­pyn­yl)oxy]tri­methyl­silane, 98%

C8H16OSi H3C
CH3
Alkynes contain a highly versatile functional group that FW 156.30 HC
O Si CH3
CH3
may be utilized for numerous reactions such as electrophilic [17869‑77‑1] CH3
additions of hydrogen, halogens, hydrogen halides, or water; 495239-5ML 5 mL
metathesis; hydroboration; oxidative cleavage; C–C coupling; and 495239-25ML 25 mL
cycloadditions. Terminal alkynes may be transformed into metal
acetylides and can then be submitted to nucleophilic substitution 1,1-Diphenyl-2-pro­pyn-1-ol, 99%
with alkyl halides, forming new C–C bonds, or nucleophilic C15H12O CH
addition, e.g., the Favorskii reaction. FW 208.26 HO C

[3923‑52‑2]
Sigma-Aldrich® furnishes a broad portfolio of alkynes consisting
of more than 250 products. To see the full listing, please visit
Functionalized Alkynes

477443-5G 5 g
the organic building blocks section on Chem Product Central at: 477443-25G 25 g
sigma-aldrich.com/chemprod.
2-Ethynyl­benzyl alcohol, 97%
From the class of cycloaddition reactions that can be performed
with alkynes, the Huisgen 1,3-dipolar cycloaddition stands out C9H8O OH

and has found tremendous interest in recent years as the best FW 132.16 CH
[10602‑08‑1]
representative of a “click” reaction. Alkyne building blocks with a
second functionality are particularly useful in click chemistry. The 520039-5G 5 g

second functional group allows the attachment of a molecule of 4-Ethynyl­benzyl alcohol, 97%
interest that subsequently can be “clicked” conveniently to the
C9H8O
target azide. The following product list contains alkynes with a free FW 132.16
CH
HO
or protected hydroxyl functional group, halogen-bearing alkynes, [10602‑04‑7]
and miscellaneous other alkynes with an additional functional group.
519235-5G 5 g

1-Ethynyl-1-cyclo­hexanol, ≥99%
Hydroxylated Alkynes C8H12O OH
CH
tert-Butyl­dimethyl(2-pro­pyn­yloxy)silane, 97% FW 124.18
[78‑27‑3]
C9H18OSi CH3 CH
3
FW 170.32 O Si CH3 E51406-5ML 5 mL
HC
[76782‑82‑6] CH3
CH3 E51406-100ML 100 mL
E51406-5L 5 L
495492-5ML 5 mL
E51406-20L 20 L
495492-25ML 25 mL
1-Ethynyl­cyclo­penta­nol, 98%
2-tert-Butyl­dimethyl­siloxy­but-3-yne, 97%
C7H10O OH
tert-Butyl-dimethyl-(methyl-prop-2-ynloxy)silane CH3
CH3 CH
O Si CH3
FW 110.15
HC
CH3
CH3 [17356‑19‑3]
CH3
130869-5G 5 g
667579-1G 1 g
667579-10G 10 g 2-(3-Fluoro­phenyl)-3-butyn-2-ol, 90%
C10H9FO CH3
4-(tert-Butyl­dimethyl­silyl­oxy)-1-butyne, 97% CH
FW 164.18
OH
C10H20OSi CH3 CH3
HC O Si CH3
FW 184.35 F
CH3 CH3
[78592‑82‑2]
648930-1G 1 g
541672-5ML 5 mL
541672-25ML 25 mL 1-Heptyn-3-ol, 97%
C7H12O HC CH3
3-Butyn-1-ol, 97%
FW 112.17 OH
C4H6O HC OH [7383‑19‑9]
FW 70.09
666963-1G 1 g
[927‑74‑2]
666963-10G 10 g
130850-5G 5 g
130850-25G 25 g 1-Hexyn-3-ol, 90%
130850-100G 100 g C6H10O CH3
HC
FW 98.14 OH
3-Butyn-2-ol, 97%
[105‑31‑7]
C4H6O OH
HC 537764-5G 5 g
FW 70.09 CH3
537764-25G 25 g
[2028‑63‑9]
447986-25ML 25 mL 5-Hexyn-1-ol, 96%
447986-100ML 100 mL C6H10O HC OH
FW 98.14
3,5-Dimethyl-1-hexyn-3-ol, 99%
[928‑90‑5]
C8H14O OH
CH3
HC 302015-1G 1 g
FW 126.20
CH3 CH3 302015-5G 5 g
[107‑54‑0]
302015-25G 25 g
278394-100ML 100 mL
278394-500ML 500 mL

TO ORDER: Contact your local Sigma-Aldrich office (see back cover),

or visit sigma-aldrich.com/chemicalsynthesis.
 15

3-Hydroxy­phenyl­acetyl­ene 2-Phenyl-3-butyn-2-ol, ≥98%

3-Ethynyl­phenol CH
C10H10O CH3
C8H6O FW 146.19 CH
OH
FW 118.13 HO [127‑66‑2]
[10401‑11‑3] 212997-5G 5 g
632023-1G 1 g 212997-25G 25 g
632023-5G 5 g 212997-100G 100 g

2-Methyl-3-butyn-2-ol, 98% 1-Phenyl-2-pro­pyn-1-ol, 98%

Dimethyl ethynyl carbinol CH3 (±)-α-Ethynyl­benzyl alcohol; (±)-3-Hydroxy-3-phenyl-1- HO
HC OH CH
C5H8O CH3 pro­pyn­e; 1-Phenyl­pro­pargyl alcohol; (±)-1-Phenyl-2-
FW 84.12 pro­pyn-1-ol

Functionalized Alkynes
[115‑19‑5] C9H8O
129763-5ML 5 mL FW 132.16
129763-100ML 100 mL [4187‑87‑5]
129763-1L 1 L 226610-1G 1 g
226610-10G 10 g
5-Methyl-1-hexyn-3-ol, 97%
C7H12O CH3 Pro­pargyl alcohol, 99%
HC
FW 112.17 OH CH3 2-Pro­pyn-1-ol HC
OH
[61996‑79‑0] C3H4O
666971-1G 1 g FW 56.06
666971-5G 5 g [107‑19‑7]
P50803-5ML 5 mL
3-Methyl-1-penten-4-yn-3-ol, 98% P50803-100ML 100 mL
Ethynyl methyl vinyl carbinol HO P50803-500ML 500 mL
C6H8O HC CH2
P50803-1L 1 L
CH3
FW 96.13
[3230‑69‑1] 1,1,1-Tri­fluoro-2-phenyl-3-butyn-2-ol, 96%
493023-5G 5 g C10H7F3O CF3
CH
FW 200.16
OH
3-Methyl-1-pentyn-3-ol, 98% [99727‑20‑5]
Ethyl ethynyl methyl carbinol; Meparfynol HO 553298-500MG 500 mg
HC CH3
C6H10O CH3 553298-1G 1 g
FW 98.14
[77‑75‑8] 3-Tri­methyl­siloxy-1-pro­pyn­e, 98%
137561-100ML 100 mL (Pro­pargyl­oxy)tri­methyl­silane; Tri­methyl(pro­pargyl­oxy) CH3

137561-500ML 500 mL silane; Tri­methyl(2-pro­pyn­yloxy)silane; HC

O Si CH3
CH3
O-(Tri­methyl­silyl)pro­pargyl alcohol
1-Octyn-3-ol, 96% C6H12OSi
C8H14O OH FW 128.24
FW 126.20 HC
CH3 [5582‑62‑7]
[818‑72‑4] 374423-1G 1 g
127280-10G 10 g 374423-10G 10 g
127280-50G 50 g
3-(Tri­methyl­silyl­oxy)-1-butyne, 97%
127280-250G 250 g
2-(Tri­methyl­silyl­oxy)-3-butyne CH3
1-Pentyn-3-ol, 98% C7H14OSi O Si CH3
HC CH3
C5H8O HC CH3 FW 142.27 CH3
FW 84.12 OH [17869‑76‑0]
[4187‑86‑4] 632031-5G 5 g
E28404-1G 1 g 632031-25G 25 g
E28404-10G 10 g
10-Undecyn-1-ol, ≥95.0% (GC)
4-Pentyn-1-ol, 97% C11H20O HC
OH
C5H8O OH FW 168.28
HC
FW 84.12 [2774‑84‑7]
[5390‑04‑5] 94195-1ML 1 mL
302481-5G 5 g
302481-25G 25 g

4-Pentyn-2-ol, ≥98%
(±)-4-Pentyn-2-ol OH
C5H8O HC CH3
FW 84.12
[2117‑11‑5]
268992-1G 1 g
268992-5G 5 g
268992-25G 25 g

Ready to scale up? For competitive quotes on larger quantities or custom synthesis,
contact your local Sigma-Aldrich office, or visit safcglobal.com.
 16

Halogenated Alkynes 3-Chloro-1-ethynyl­ben­zene, 97%

C8H5Cl
(3,5-Bis(tri­fluoro­methyl)phenyl­ethynyl)tri­methyl­silane, 97% FW 136.58
CH

C13H12F6Si F3C [766‑83‑6] Cl

CH3
FW 310.31 Si CH3 630268-1G 1 g
[618092‑28‑7] CH3 630268-5G 5 g
F3C

597805-5G 5 g 6-Chloro-1-hexyne, 98%

1-Bromo-2-butyne, 99% C6H9Cl HC Cl
FW 116.59
C4H5Br H3C
[10297‑06‑0]
Br
FW 132.99
469777-5ML 5 mL
[3355‑28‑0]
Functionalized Alkynes

469777-25ML 25 mL
427292-1G 1 g
427292-5G 5 g 3-Chloro-3-methyl-1-butyne, 97%
1-Bromo-2-ethynyl­ben­zene, 95% C5H7Cl CH3
HC Cl
FW 102.56
C8H5Br [1111‑97‑3]
CH3
CH
FW 181.03
301345-1G 1 g
[766‑46‑1] Br
301345-5G 5 g
494178-1G 1 g
301345-25G 25 g
1-Bromo-4-ethynyl­ben­zene, 97% 1-Chloro-2-octyne, 98%
C8H5Br Br CH C8H13Cl Cl
FW 181.03 FW 144.64
CH3(CH2)3CH2

[766‑96‑1] [51575‑83‑8]
206512-1G 1 g
442860-1G 1 g
1-Bromo-2-pentyne, 97% 442860-10G 10 g

C5H7Br Br 5-Chloro-1-pentyne, 98%

FW 147.01 H3C
C5H7Cl Cl
HC
[16400‑32‑1] FW 102.56
429538-1G 1 g [14267‑92‑6]
429538-10G 10 g
244376-5G 5 g
(2-Bromo­phenyl­ethynyl)tri­methyl­silane, 98% 244376-25G 25 g

C11H13BrSi CH3 (5-Chloro-1-pentynyl)tri­methyl­silyl­silane, 97%

FW 253.21 Si CH3
CH3 1-Chloro-5-tri­methyl­silyl-4-pentyne Cl
CH3
[38274‑16‑7] Br C8H15ClSi Si CH3
484695-5G 5 g CH3
FW 174.74
[77113‑48‑5]
(3-Bromo­phenyl­ethynyl)tri­methyl­silane, 97%
595918-5G 5 g
C11H13BrSi CH3
FW 253.21 Si CH3
1-Chloro-4-(phenyl­ethynyl)ben­zene, 98%
CH3
[3989‑13‑7] Br C14H9Cl Cl
510971-5G 5 g FW 212.67
[5172‑02‑1]
(4-Bromo­phenyl­ethynyl)tri­methyl­silane, 98%
510750-1G 1 g
C11H13BrSi CH3
510750-5G 5 g
FW 253.21 Br Si CH3
CH3
[16116‑78‑2] (3-Chloro­phenyl­ethynyl)tri­methyl­silane, 98%
494011-5G 5 g C11H13ClSi CH3
494011-25G 25 g Si CH3
FW 208.76
CH3
[227936‑62‑1] Cl
1-Chloro-2-ethynyl­ben­zene, 98%
597708-1G 1 g
(2-Chloro­phenyl)acetyl­ene CH 597708-5G 5 g
C8H5Cl
FW 136.58 Cl
(4-Chloro­phenyl­ethynyl)tri­methyl­silane, 97%
[873‑31‑4] C11H13ClSi CH3
465305-1G 1 g FW 208.76 Cl Si CH3
465305-5G 5 g CH3
[78704‑49‑1]
1-Chloro-4-ethynyl­ben­zene, 98% 563447-5G 5 g
563447-25G 25 g
(4-Chloro­phenyl)acetyl­ene Cl CH
C8H5Cl 1,4-Dichloro-2-butyne, 99%
FW 136.58 C4H4Cl2 Cl
[873‑73‑4] FW 122.98 Cl
206474-1G 1 g [821‑10‑3]
D59607-5G 5 g
D59607-25G 25 g
D59607-100G 100 g

TO ORDER: Contact your local Sigma-Aldrich office (see back cover),

or visit sigma-aldrich.com/chemicalsynthesis.
 17

3,4-Dichloro­phenyl­acetyl­ene, 97% 1-Ethynyl-2-fluoro­ben­zene, 97%

1,2-Dichloro-4-ethynyl­ben­zene; 3,4-Dichloro- Cl CH
C8H5F
CH
1-ethynyl­ben­zene FW 120.12
C8H4Cl2 Cl [766‑49‑4] F

FW 171.02 467006-250MG 250 mg

[556112‑20‑0] 467006-1G 1 g
672890-1G 1 g
1-Ethynyl-3-fluoro­ben­zene, 98%
(2,4-Difluoro­phenyl­ethynyl)tri­methyl­silane, 96% C8H5F
CH
C11H12F2Si CH3 FW 120.12
F Si CH3
FW 210.30 [2561‑17‑3] F
CH3
[480438‑92‑4] F 519405-5G 5 g

Functionalized Alkynes
563471-1ML 1 mL
563471-5ML 5 mL
1-Ethynyl-4-fluoro­ben­zene, 99%
C8H5F F CH
(3,5-Difluoro­phenyl­ethynyl)tri­methyl­silane, 98% FW 120.12
C11H12F2Si F
CH3
[766‑98‑3]
FW 210.30 Si CH3 404330-1G 1 g
[445491‑09‑8] CH3 404330-5G 5 g
F

589330-5G 5 g 4-Ethynyl-1-fluoro-2-methyl­ben­zene, 97%

1-Ethynyl-3,5-bis(tri­fluoro­methyl)ben­zene, 97% C9H7F H3C

FW 134.15 F CH
C10H4F6 F3C
[351002‑93‑2]
FW 238.13 CH
521205-1G 1 g
[88444‑81‑9]
F3C 521205-5G 5 g

630241-1G 1 g 2-Ethynyl-α,α,α-tri­fluoro­tolu­ene, 97%

1-Ethynyl-2,4-difluoro­ben­zene, 97% 1-Ethynyl-2-tri­fluoro­methyl­ben­zene
CH
C9H5F3
C8H4F2 F CH FW 170.13 CF3
FW 138.11
[704‑41‑6]
[302912‑34‑1] F
521183-1G 1 g
556440-5G 5 g
3-Ethynyl-α,α,α-tri­fluoro­tolu­ene, 97%
1-Ethynyl-3,5-difluoro­ben­zene, 97%
C9H5F3
C8H4F2 F CH
FW 170.13
FW 138.11 F3C
CH [705‑28‑2]
[151361‑87‑4]
F 557331-5G 5 g
590177-1G 1 g

Now Available!
The New ISOTEC® 2008–2010 Stable Isotopes Catalog
from Aldrich Chemistry
• More than 750 new products
• Over 3,000 chemical listings
• 13
C, 15N, D, 18O, 17O labeled products
• Enriched noble gases
• Application sections and literature references

To receive your FREE copy of the catalog, visit sigma-aldrich.com/sicat

sigma-aldrich.com

Ready to scale up? For competitive quotes on larger quantities or custom synthesis,
contact your local Sigma-Aldrich office, or visit safcglobal.com.
 18

4-Ethynyl-α,α,α-tri­fluoro­tolu­ene, 97% 1-[(Tri­methyl­silyl)ethynyl]-4-(tri­fluoro­methyl)ben­zene, 97%

C9H5F3 F3C CH
[4-(Tri­fluoro­methyl)phenyl](tri­methyl­silyl)acetyl­ene CH3
FW 170.13 C12H13F3Si F3C Si CH3

[705‑31‑7] FW 242.31 CH3

556432-5G 5 g [40230‑95‑3]

563439-5ML 5 mL
(2-Fluoro­phenyl­ethynyl)tri­methyl­silane, 96% 563439-25ML 25 mL
C11H13FSi CH3
Si CH3
FW 192.30
[480439‑33‑6] F
CH3 Miscellaneous Alkynes
571407-5G 5 g N-tert-Amyl-1,1-dimethyl­pro­pargyl­amine, 98%
571407-25G 25 g
Functionalized Alkynes

C10H19N H
N
CH3

FW 153.26 HC CH3
(4-Fluoro­phenyl­ethynyl)tri­methyl­silane, 97%
H3C CH3 CH3
C11H13FSi CH3
[2978‑40‑7]
F Si CH3 514934-5G 5 g
FW 192.30
CH3
[130995‑12‑9]
N-tert-Butyl-1,1-dimethyl­pro­pargyl­amine, 97%
563463-5ML 5 mL
C9H17N H
N CH3
563463-25ML 25 mL
FW 139.24 HC
CH3
H3C CH3 CH3
(4-Iodo­phenyl­ethynyl)tri­methyl­silane, 97% [1118‑17‑8]
C11H13ISi CH3 513695-5G 5 g
I Si CH3
FW 300.21
CH3 Cyclo­pro­pyl­acetyl­ene, 97%
[134856‑58‑9]
Ethynyl­cyclo­propane HC
640751-1G 1 g
C5H6
640751-5G 5 g
FW 66.10
Pro­pargyl bro­mide solution [6746‑94‑7]
3-Bromo-1-pro­pyn­e HC 663018-5G 5 g
Br 663018-25G 25 g
C3H3Br
FW 118.96
1,3-Di­ethynyl­ben­zene, 97%
[106‑96‑7]
C10H6 CH
 80 wt. % in xylene FW 126.15
530409-50G 50 g [1785‑61‑1]
HC
530409-125G 125 g
632104-1G 1 g
Pro­pargyl chloride, 98% 632104-5G 5 g
3-Chloro-1-pro­pyn­e HC
1,4-Di­ethynyl­ben­zene, 96%
Cl
C3H3Cl
FW 74.51 C10H6
HC CH
[624‑65‑7] FW 126.15
[935‑14‑8]
143995-5G 5 g
632090-5G 5 g
143995-25G 25 g

Pro­pargyl chloride solution 3-Dimethyl­amino-1-pro­pyn­e, 97%

N,N-Dimethyl­pro­pargyl­amine; CH3
3-Chloro-1-pro­pyn­e HC
N,N-Dimethyl-2-pro­pyn­yl­amine N
C3H3Cl Cl HC CH3
C5H9N
FW 74.51
FW 83.13
[624‑65‑7]
[7223‑38‑3]
 70 wt. % in toluene 143065-5G 5 g
384321-100ML 100 mL 143065-25G 25 g

4-(Tri­fluoro­methoxy) phenyl­acetyl­ene, 97% 1,1-Dimethyl-N-tert-octyl­pro­pargyl­amine, 96%

4-Ethynyl-1-(tri­fluoro­methoxy) ben­zene F3CO CH C13H25N H CH3
N CH3
C9H5F3O FW 195.34 HC
CH3
H3C CH3 CH3 CH3
FW 186.13 [263254‑99‑5]
[160542‑02‑9] 513709-1G 1 g
672858-1G 1 g
2-Ethynyl­ani­line, 98%
1-[(Tri­methyl­silyl)ethynyl]-3-fluoro­ben­zene, 97% C8H7N CH
C11H13FSi CH3 FW 117.15
FW 192.30 Si CH3 NH2
[52670‑38‑9]
CH3
[40230‑96‑4] F 597651-1G 1 g
563269-5G 5 g 597651-5G 5 g

1-[(Tri­methyl­silyl)ethynyl]-3-(tri­fluoro­methyl)ben­zene, 98% 3-Ethynyl­ani­line, ≥98%

1-(3’-Tri­fluoro­methyl­phenyl)-2-(tri­methyl­silyl)acetyl­ene C8H7N CH
C12H13F3Si CH3
FW 117.15
Si CH3
FW 242.31 [54060‑30‑9] H2N
CH3
[40230‑93‑1] F3C
498289-5G 5 g
562661-5ML 5 mL
562661-25ML 25 mL

TO ORDER: Contact your local Sigma-Aldrich office (see back cover),

or visit sigma-aldrich.com/chemicalsynthesis.
 19

4-Ethynyl­ani­line, 97% 2-Methyl-3-butyn-2-amine, 95% 8

1-Amino-4-ethynyl­ben­zene H2N CH
3-Amino-3-methyl-1-butyne; NH2
HC CH3
C8H7N 1,1-Dimethyl­pro­pargyl­amine
CH3
FW 117.15 C5H9N
[14235‑81‑5] FW 83.13
481122-5G 5 g [2978‑58‑7]
687189-5G 5 g
4-Ethynyl­biphenyl, 97%
C14H10 N-Methyl­pro­pargyl­amine, 95%
CH
FW 178.23 3-Methyl­amino-1-pro­pyn­e H
N
[29079‑00‑3] C4H7N HC CH3

521175-5G 5 g FW 69.11

Functionalized Alkynes
[35161‑71‑8]
1-Ethynyl­cyclo­hex­ene, 99% 150223-1G 1 g
C8H10 CH 150223-5G 5 g
FW 106.17
[931‑49‑7] N-Methyl-N-pro­pargyl­benzyl­amine, 97%
316571-5G 5 g Pargyline N
CH

316571-25G 25 g C11H13N CH3

FW 159.23
1-Ethynyl­cyclo­hexyl­amine, 98% [555‑57‑7]
C8H13N NH2 M74253-5G 5 g
CH
FW 123.20 M74253-25G 25 g
[30389‑18‑5]
1,8-Nona­diyne, 98%
177024-1G 1 g
177024-5G 5 g C9H12 HC CH
FW 120.19
1-Ethynyl-3,5-dimethoxy­ben­zene [2396‑65‑8]
C10H10O2 H3CO 161306-10G 10 g
FW 162.19 CH
[171290‑52‑1] 1,7-Octa­diyne, 98%
H3CO
98% (CP) C8H10 HC
CH

FW 106.17
588520-1G 1 g
[871‑84‑1]
588520-5G 5 g
161292-1G 1 g
4-Ethynyl-N,N-dimethyl­ani­line, 97% 161292-10G 10 g
4-Dimethyl­amino­phenyl­acetyl­ene; H3C
Pro­pargyl­amine, 98%
N CH
1-Ethynyl-4-dimethyl­ani­line H3C
C10H11N 3-Amino-1-pro­pyn­e; 2-Pro­pyn­yl­amine HC
NH2
FW 145.20 C3H5N
[17573‑94‑3] FW 55.08
[2450‑71‑7]
592609-1G 1 g
592609-5G 5 g P50900-1G 1 g
P50900-5G 5 g
1-Ethynyl-2-nitro­ben­zene, 98% P50900-25G 25 g
C8H5NO2 CH
Pro­pargyl­amine hydrochloride, 95%
FW 147.13
[16433‑96‑8] NO2 3-Amino-1-pro­pyn­e hydrochloride; HC • HCl
NH2
2-Pro­pyn­yl­amine hydrochloride
519456-5G 5 g
C3H5N · HCl
1-Ethynyl-4-nitro­ben­zene, 97% FW 91.54
[15430‑52‑1]
C8H5NO2 O2N CH
FW 147.13 P50919-1G 1 g
[937‑31‑5] P50919-10G 10 g

519294-1G 1 g Tri­pro­pargyl­amine, 98%

519294-5G 5 g
C9H9N N
CH
HC CH
1-Ethynyl-4-phen­oxy­ben­zene, 97% FW 131.17
[6921‑29‑5]
C14H10O HC O
FW 194.23 T84964-5G 5 g
[4200‑06‑0]
521213-1G 1 g
521213-5G 5 g

1,6-Hepta­diyne, 97%
C7H8 HC CH
FW 92.14
[2396‑63‑6]
407437-1G 1 g

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