Silver-catalyzed nitrogenation of alkynes: A direct approach to nitriles through C≡C bond cleavage

Article abstract of DOI:10.1002/anie.201300193

Three in one blow! A novel direct transformation of alkynes into nitriles by a silver-catalyzed nitrogenation reaction through C≡C bond cleavage has been developed. This research provides both a new application for alkynes in organic synthesis, and valuable mechanistic insights into nitrogenation chemistry. Copyright

Full text of DOI:10.1002/anie.201300193

Angewandte
Chemie
DOI: 10.1002/anie.201300193
Carbon–Carbon Bond Cleavage
Silver-Catalyzed Nitrogenation of Alkynes: A Direct Approach to
ꢀ
Nitriles through C C Bond Cleavage**
Tao Shen, Teng Wang, Chong Qin, and Ning Jiao*
Dedicated to Professor Manfred T. Reetz on the occasion of his 70th birthday
À
The transformation of alkynes is a fundamental method that
has been widely used in organic synthesis.[1–11] Alkyne
chemistry can be dated back to the early nineteenth century.
The hydration of alkynes to ketones[1] (Scheme 1a) and the
addition reactions of alkynes[2] (Scheme 1b) are early exam-
ples. Subsequently, various catalytic systems were developed.
For example, the Pd-catalyzed Wacker-type oxidation[3,4] to
generate 1,2-diketones (Scheme 1c) is one of the most
important industrial processes. The development of cycliza-
tion reactions[5] such as click chemistry (Scheme 1d)[6] has
established new perspectives for the use of alkynes in drug
discovery, materials science, supramolecular chemistry, poly-
mer chemistry, and biotechnology.[7] Furthermore, the cou-
pling of terminal alkynes, such as the Sonogashira coupling
(Scheme 1e), provides important methods for C C bond
formation.[8] The catalytic cleavage of C C bonds to produce
ꢀ
carboxylic acids[9] and new alkynes[10] has also been disclosed
(Scheme 1 f,g). Because of the significance and wide applica-
tions of such chemistry in organic synthesis, the exploration
for new types of alkyne transformations is very attractive to
researchers.
Nitriles[11] are one of the most common structural motifs
in nature, and are versatile building blocks in the synthesis of
natural products, pharmaceuticals, agricultural chemicals,
materials, and dyes. Their importance in synthetic and
medicinal chemistry has attracted considerable attention for
the development of new synthetic strategies for these com-
pounds.[12–15] Azides have been widely used in organic
reactions,[16–18] but recent progress on the direct transforma-
tion of simple hydrocarbons into N-containing compounds[18]
through a nitrogenation strategy encouraged us to try the
direct transformation of alkynes. Although metal-catalyzed
ꢀ
C C bond cleavage involving alkyne metathesis has been
disclosed,[9,10] direct C C bond cleavage to form nitriles
ꢀ
(Scheme 1h) is still unknown and remains both challenging
and of great value.
Herein, we report a novel and direct silver-catalyzed
ꢀ
nitrogenation reaction of alkynes to nitriles through C C
bond cleavage (Scheme 1h). The significance of the present
chemistry is threefold: 1) It is the first example of a direct
transformation from terminal alkynes to nitriles. 2) The
À
application of selective C C bond cleavage in organic syn-
thesis presents one of the most attractive and challenging
À
projects. This chemistry provides a novel means of C C bond
cleavage. 3) Compared to traditional gold salt p-acid cata-
lysts,[19] the silver catalyst plays a key role in this trans-
formation. This research not only provides a new application
for alkynes in organic synthesis, but also offers valuable
mechanistic insights into this novel nitrogenation chemistry,
which may promote the discovery of other new types of
nitrogenation reactions for the construction of N-containing
compounds.
The initially investigated substrate for the direct nitro-
genation of acetylenes was para-methoxy phenylacetylene.
When the reaction is performed in the presence of Ag2CO3
using azidotrimethylsilane (TMSN3) as the nitrogen source,
p-methoxy-benzonitrile (2a) was obtained in 58% yield
(Table 1, entry 1). Reactions catalyzed by other transition
metals, such as AuCl3, NiCl2, FeCl2, Cu(OAc)2, and Pd(OAc)2,
either did not proceed or gave poor yields (Table 1, entries 2
and 3; see also the Supporting Information). Product 2a was
obtained in 81% yield when DMSO was employed as the
Scheme 1. Direct transformations of alkynes.
[*] T. Shen, T. Wang, C. Qin, Dr. N. Jiao
State Key Laboratory of Natural and Biomimetic Drugs
School of Pharmaceutical Sciences, Peking University
Xue Yuan Rd. 38, Beijing 100191 (China)
E-mail: jiaoning@bjmu.edu.cn
Dr. N. Jiao
State Key Laboratory of Organometallic Chemistry
Chinese Academy of Sciences, Shanghai 200032 (China)
[**] Financial support from the National Basic Research Program of
China (973 Program; 2009CB825300) and the National Science
Foundation of China (21172006) are greatly appreciated. We thank
Xiaoqiang Huang for reproducing the results of 2a and 4i.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201300193.
Angew. Chem. Int. Ed. 2013, 52, 1 – 5
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1
These are not the final page numbers!

.
Angewandte
Communications
Table 1: Reaction optimization for the direct conversion of p-methoxy
phenylacetylene 1a into nitrile 2a.[a]
Entry
Catalyst
[N] source
solvent
Yield of 2a [%][b]
1
2
3
Ag2CO3
AuCl3
NiCl2
TMSN3
TMSN3
TMSN3
TMSN3
TMSN3
TMSN3
TMSN3
NaN3
TsN3
DPPA
TMSN3
TMSN3
TMSN3
TMSN3
DMF
DMF
DMF
58
0
0
68
81
0
4[c]
5
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
–
DMSO
DMSO
HOAc
TFA
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
6
7
8
9
10
11
12[d]
13[e]
14[f]
0
trace
0
0
0
62
60
84
Ag2CO3
Ag2CO3
Ag2CO3
[a] Reaction conditions: 1a (0.5 mmol), catalyst (0.05 mmol), TMSN3
(1.0 mmol), solvent (2 mL), stirred at 808C under air for 12 h. [b] Yield of
isolated products. [c] The reaction was carried out at 1308C. [d] 5 mol%
of Ag2CO3 was used. [e] The reaction was carried out under Ar.
[f] 4.0 equiv of TMSN3 was used. Ac=acetyl, DMF=dimethylforma-
mide, DMSO=dimethylsulfoxide, DPPA=diphenylphosphoryl azide,
TFA=trifluoroacetic acid, TMS=trimethylsilyl.
Scheme 2. Direct conversion of aryl alkynes 1 into nitriles 2. Standard
conditions: 1 (0.5 mmol), TMSN3 (1.0 mmol), and Ag2CO3
(0.05 mmol) in DMSO (2 mL) at 1008C under air for 12 h. Yields
shown are of isolated products. [a] These reactions were carried out at
808C for 24 h. Bn=benzyl, Boc=tert-butoxycarbonyl, DMSO=di-
methylsulfoxide, MOM=methoxymethyl.
solvent (Table 1, entry 5). In contrast, other solvents such as
acetic acid and trifluoroacetic acid (TFA) did not perform
well (Table 1, entries 6 and 7). Other azide reagents such as
diphenylphosphoryl azide (DPPA), NaN3, and p-tosyl azide
did not yield the desired products (Table 1, entries 8–10).
The scope of the transformation was then investigated
under the standard conditions (Table 1, entry 5). Phenyl-
acetylenes bearing electron-donating substituents (MeO,
EtO, BocN, Me, and tBu) afforded the desired products in
good to excellent yields (Scheme 2, 2a–2c, 2e–2g, 2j, 2k, and
2n). Halo-substituted phenylacetylenes worked well to pro-
duce the corresponding halo-substituted benzonitriles, which
could be used in further coupling reactions (Scheme 2, 2d, 2l,
and 2p). Some substrates with unprotected reactive groups,
such as NH2 and NH, are well tolerated (2t, 2u, and 2y).
Heteroaryl-substituted substrates could also be converted
into the desired products in moderate yields (2s and 2y).
Moreover, the alkenyl nitrile product 2v was also obtained in
73% yield.
yields, respectively (see Eq. (S1-2) in the Supporting Infor-
mation), which may exclude a radical process in this trans-
formation. During the reaction, a key intermediate, vinyl
azide 5, was observed and characterized (Scheme 4a). This
species can be directly transformed into nitrile product 2a in
81% yield under the standard conditions (Scheme 4b). In
contrast, 2a was obtained in only 11% yield in the absence of
TMSN3, which indicates that another equivalent of TMSN3
ꢀ
plays an important role in C C bond cleavage (Scheme 4b).
A catalytic amount of TMSN3 is enough to enable the
conversion of 5 into 2a (Scheme 4b). It can thus be concluded
that the conversion from vinyl azide 5 into nitrile 2a does not
To our delight, aliphatic alkynes could be smoothly
converted into the expected alkyl nitriles in moderate to
excellent yields (Scheme 3). A substrate bearing a strongly
coordinating sulfur atom did not inhibit this Ag catalysis
ꢀ
(Scheme 3, 4d). Substrates with double C C bonds, such as
octa-1,7-diyne, produced 4h in 54% yield. The long-chain
alkyl alkyne dec-1-yne was converted into 4i in better yield
(96%) than other, shorter chain, alkyl alkynes (4 f and 4g).
To further probe the mechanism, control experiments
with possible intermediates were designed and investigated.
The reactions performed well in the presence of TEMPO or
BHT producing the desired product 2a in 77% and 72%
Scheme 3. Direct conversion of alkyl alkynes 3 into aliphatic nitriles
4.[a] These reactions were carried out at 1008C under air for 12 h.
Unless otherwise noted yields shown are based on NMR spectroscopy.
[b]Yield of isolated products. [c] 4.0 equiv of TMSN3 was used.
2
www.angewandte.org
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2013, 52, 1 – 5
These are not the final page numbers!

Angewandte
Chemie
Scheme 5. Proposed mechanism.
Scheme 4. Mechanistic studies and control experiments.
On the basis of these preliminary results, possible
mechanisms are proposed (Scheme 5). Initially, the alkyne is
activated by the silver catalyst. Subsequent attack by azide
anion generates trans-alkenyl metal complexe B. The proto-
nation of B generates vinyl azide C with a trace amount of
H2O in the DMSO solvent, which was supported by an
exchange experiment in the presence of D2O (see the
Supporting Information). Next, vinyl azide C cyclizes with
azide like traditional click reaction to form the unstable
intermediate D (Scheme 5).[21] Although the rearrangement
of intermediate D could occur and produce tetrazole E in
conjunction with the release of CH2N2,[21] the control experi-
ment excludes the conversion of tetrazole E into nitrile
require the silver catalyst (Scheme 4b). Furthermore, when
3-(4-methoxyphenyl)-2H-azirine (6), which is potentially
generated by the nitrene intermediate,[20] and tetrazole 7
[21,22]
were employed as the substrates, the reactions did not
proceed (Scheme 4c and d). These results exclude azirine and
tetrazole as intermediates in this transformation.
To gain additional insight, the reaction of 1a under
standard reaction conditions in [D6]DMSO was monitored by
1H NMR spectroscopy (Figure 1). By comparison with stan-
dard samples in [D6]DMSO (see the Supporting Informa-
tion), the signal at 4.0 ppm (0–1.5 h) was assigned to 1a. After
reacting with TMSN3 for 10 min, the weak signals at 4.93 and
5.53 ppm were assigned to the olefinic hydrogen of vinyl azide
5, which reached a peak after 1.5 h (Figure 1). The signals at
7.7, 7.1, and 3.8 ppm were assigned to the nitrile product 2a,
which appeared and increased after 10 min along with the
decrease of 1a. The peaks of vinyl azide 5 became weak at
3.5 h, and completely disappeared at 6.5 h as it was converted
into nitrile product 2a (Figure 1).
product
2
under the standard reaction conditions
(Scheme 4d). Therefore, the direct transformation of inter-
mediate D into nitrile product 2 through a fast rearrangement
process that releases HN3 and CH2N2, which were detected by
GC-MS (see the Supporting Information), is proposed. In the
last step, the HN3 produced is reused in the cyclization step of
C to produce D.
In summary, we have demonstrated the first direct
conversion of alkynes into nitriles by Ag-catalyzed nitro-
ꢀ
genation of alkynes through C C bond cleavage. From the
results of the present study, and on the basis of the proposed
mechanism, it should be possible to develop novel chemical
À
transformations through C C bond cleavage, which should be
of interest to both industrial and academic researchers.
Received: January 9, 2013
Revised: February 28, 2013
Published online: && &&, &&&&
Keywords: alkynes · azides · nitriles · rearrangement · silver
.
[1] a) Organic Reactions, Wiley, Hoboken, 1994, 46; b) M. Oes-
treich, Sci. Synth. 2006, 25, 199; c) G. Schilling, GIT Labor-
Fachz. 2003, 47, 621.
Figure 1. Reaction of 1a monitored by 1H NMR spectroscopy
(400 MHz, [D6]DMSO). A=1a alkynyl group, B=1a methoxy group,
[2] For reviews, see: a) H. Takaya, R. Noyori, Comprehensive
Organic Synthesis (Ed.: B. M. Trost, I. Fleming), Pergamon,
Oxford, 1991; b) S. Nishimura, Handbook of Heterogeneous
À
À
À
C=1a Ar H, D=5 alkenyl group, E=5 Ar H, F=2a Ar H, G=2a
methoxy group.
Angew. Chem. Int. Ed. 2013, 52, 1 – 5
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
3
These are not the final page numbers!

.
Angewandte
Communications
Catalytic Hydrogenation for Organic Synthesis, Wiley-Inter-
science, New York, 2001.
Angew. Chem. 2010, 122, 6772; Angew. Chem. Int. Ed. 2010, 49,
6622; e) J.-L. He, K. Yamaguchi, N. Mizuno, J. Org. Chem. 2011,
76, 4606; f) S. Sasson, S. Rozen, Org. Lett. 2005, 7, 2177; g) S.
Chiba, L. Zhang, G. Y. Ang, B. W.-Q. Hui, Org. Lett. 2010, 12,
2052; h) R. Tanaka, K. Yamabet, J. Chem. Soc. Chem. Commun.
1983, 329.
[3] For recent reviews, see: a) A. H. Haines, Methods for the
Oxidation of Organic Compounds. Alkanes, Alkenes, Alkynes,
and Arenes, Academic Press, New York, 1985; b) M. Jacques, J.
Mol. Catal. A: Chem. 2011, 338, 7; c) J. M. Takacs, X. Jiang, Curr.
Org. Chem. 2003, 7, 369; d) C. N. Cornell, M. S. Sigman, Inorg.
Chem. 2007, 46, 1903; e) V. Kotov, C. C. Scarborough, S. S. Stahl,
Inorg. Chem. 2007, 46, 1910.
[4] For some selected examples, see: a) W. Ren, Y. Xia, S.-J. Ji, Y.
Zhang, X. Wan, J. Zhao, Org. Lett. 2009, 11, 1841; b) Z.-H. Wan,
C. D. Jones, D. Mitchell, J. Y. Pu, T. Y. Zhang, J. Org. Chem.
2006, 71, 826; c) S. Dayan, I. Ben-David, S. Rozen, J. Org. Chem.
2000, 65, 8816; d) C.-Fu. Xu, M. Xu, Y.-X. Jia, C.-Y. Li, Org. Lett.
2011, 13, 1556.
[5] K. Gilmore, I. V. Alabugin, Chem. Rev. 2011, 111, 6513.
[6] a) A. Franck, J. H. Cho, R. F. Schinazi, Chem. Rev. 2009, 109,
4207; b) “1,3-Dipolar Cycloadditions-Introduction, Survey,
Mechanism”: R. Huisgen in 1,3-Dipolar Cycloaddition Chemis-
try (Ed.: A. Padwa), Wiley, New York, 1984; c) H. C. Kolb, M. G.
Finn, K. B. Sharpless, Angew. Chem. 2001, 113, 2056; Angew.
Chem. Int. Ed. 2001, 40, 2004; d) J. E. Hein, V. V. Fokin, Chem.
Soc. Rev. 2010, 39, 1302; e) M. Meldal, C. W. Tornoe, Chem. Rev.
2008, 108, 2952; f) Z. P. Demko, K. B. Sharpless, Angew. Chem.
2002, 114, 2214; Angew. Chem. Int. Ed. 2002, 41, 2110.
[7] For selected reviews, see: a) W. H. Binder, R. Sachsenhofer,
Macromol. Rapid Commun. 2007, 28, 15; b) E. M. Sletten, C. R.
Bertozzi, Acc. Chem. Res. 2011, 44, 666; c) Click Chemistry for
Biotechnology and Materials Science (Ed.: J. Lahann), Wiley,
Chichester, 2009.
[15] a) C. W. Liskey, X. Liao, J. F. Hartwig, J. Am. Chem. Soc. 2010,
132, 11389; b) Z. Zhao, Z. Li, Eur. J. Org. Chem. 2010, 5460;
c) M. Shevlin, Tetrahedron Lett. 2010, 51, 4833; d) Z. Zhang, Z.
Wang, R. Zhang, K. Ding, Angew. Chem. 2010, 122, 6898;
Angew. Chem. Int. Ed. 2010, 49, 6746; e) H.-Q. Do, O. Daugulis,
Org. Lett. 2010, 12, 2517; f) S. Arai, Y. Koike, A. Nishida, Adv.
Synth. Catal. 2010, 352, 893; g) S. Ushijima, H. Togo, Synlett
À
2010, 1562; for a CH2CN source from isoxazole fragmentation,
see: h) J. Velcicky, A. Soicke, R. Steiner, H.-G. Schmalz, J. Am.
Chem. Soc. 2011, 133, 6948; i) T. Tanase, M. Mocnizuki, R. Sato,
V. Yamamoto, J. Organomet. Chem. 1994, 466, 233.
[16] For selected reviews, see: a) S. Brꢁse, C. Gil, K. Knepper, V.
Zimmermann, Angew. Chem. 2005, 117, 5320; Angew. Chem. Int.
Ed. 2005, 44, 5188; b) E. F. V. Scriven, K. Turnbull, Chem. Rev.
1988, 88, 297; c) S. Lang, J. A. Murphy, Chem. Soc. Rev. 2006, 35,
146; d) T. G. Driver, Org. Biomol. Chem. 2010, 8, 3831; e) S.
Chiba, Synlett 2012, 21.
[17] For selected recent examples, see: a) H. Lu, H. Jiang, L. Wojtas,
X. P. Zhang, Angew. Chem. 2010, 122, 10390; Angew. Chem. Int.
Ed. 2010, 49, 10192; b) W. Yao, L. Pan, Y. Zhang, G. Wang, X.
Wang, C. Ma, Angew. Chem. 2010, 122, 9396; Angew. Chem. Int.
Ed. 2010, 49, 9210; c) S. Chiba, L. Zhang, J.-Y. Lee, J. Am. Chem.
Soc. 2010, 132, 7266; d) J. Y. Kim, S. H. Park, J. Ryu, S. H. Cho,
S. H. Kim, S. Chang, J. Am. Chem. Soc. 2012, 134, 9110; e) K.
Weidner, A. Giroult, P. Panchaud, P. Renaud, J. Am. Chem. Soc.
2010, 132, 17511; f) Y.-F. Wang, K. K. Toh, J.-Y. Lee, S. Chiba,
Angew. Chem. 2011, 123, 6049; Angew. Chem. Int. Ed. 2011, 50,
5927; g) K. Sun, S. Liu, P. M. Bec, T. G. Driver, Angew. Chem.
2011, 123, 1740; Angew. Chem. Int. Ed. 2011, 50, 1702; h) I.
Cano, E. ꢂlvarez, M. C. Nicasio, P. J. Perꢃz, J. Am. Chem. Soc.
2011, 133, 191; i) B. J. Stokes, S. Liu, T. G. Driver, J. Am. Chem.
Soc. 2011, 133, 4702; j) J. Bonnamour, C. Bolm, Org. Lett. 2011,
13, 2012; k) S. Zhang, J. Zhao, W.-X. Zhang, Z. Xi, Org. Lett.
2011, 13, 1626; l) J. Wang, J. Wang, Y. Zhu, P. Lu, Y. Wang, Chem.
Commun. 2011, 47, 3275; m) Z. Chen, C. Ye, L. Gao, J. Wu,
Chem. Commun. 2011, 47, 5623; n) B. Lu, Y. Luo, L. Liu, L. Ye,
Y. Wang, L. Zhang, Angew. Chem. 2011, 123, 8508; Angew.
Chem. Int. Ed. 2011, 50, 8358; o) A. Wetzel, F. Gagosz, Angew.
Chem. 2011, 123, 7492; Angew. Chem. Int. Ed. 2011, 50, 7354;
p) Q. Nguyen, K. Sun, T. G. Driver, J. Am. Chem. Soc. 2012, 134,
7262; q) Z.-Y. Yan, Y. Xiao, L. Zhang, Angew. Chem. 2012, 124,
8752; Angew. Chem. Int. Ed. 2012, 51, 8624; r) T. Miura, Y.
Funakoshi, M. Morimoto, T. Biyajima, M. Murakami, J. Am.
Chem. Soc. 2012, 134, 17440; s) M. Zibinsky, V. V. Fokin, Angew.
Chem. 2013, 125, 1547; Angew. Chem. Int. Ed. 2013, 52, 1507;
t) D. Lubriks, I. Sokolovs, E. Suna, J. Am. Chem. Soc. 2012, 134,
15436.
[8] For selected reviews, see: a) R. Chinchilla, C. Najera, Chem. Rev.
2007, 107, 874; b) A. S. Dudnik, V. Gevorgyan, Angew. Chem.
2010, 122, 2140; Angew. Chem. Int. Ed. 2010, 49, 2096.
ꢀ
[9] For examples of C C bond cleavage, not using alkyne meta-
thesis, see: a) T. Shimada, Y. Yamamoto, J. Am. Chem. Soc. 2003,
125, 6646; b) S. Datta, C.-L. Chang, K.-L. Yeh, R.-S. Liu, J. Am.
Chem. Soc. 2003, 125, 9294; c) Y. Liu, F. Song, S. Guo, J. Am.
Chem. Soc. 2006, 128, 11332; d) A. Wang, H. Jiang, J. Am. Chem.
Soc. 2008, 130, 5030.
[10] For selected reviews, see: a) A. Fꢀrstner, P. W. Davies, Chem.
Commun. 2005, 2307; b) H. Villar, F. Marcus, C. Bolm, Chem.
Soc. Rev. 2007, 36, 55; c) P. H. Deshmukh, S. Blechert, Dalton
Trans. 2007, 2479, and references therein; d) W. Zhang, J. S.
Moore, Adv. Synth. Catal. 2007, 349, 93.
[11] a) A. J. Fatiadi in Preparation and Synthetic Applications of
Cyano Compounds (Ed.: S. Patai, Z. Rappaport), Wiley, New
York, 1983; b) R. C. Larock, Comprehensive Organic Trans-
formations, VCH, New York, 1989; c) A. Kleemann, J. Engel, B.
Kutscher, D. Reichert, Pharmaceutical Substances: Synthesis
Patents, Applications, 4th ed., Thieme, Stuttgart, 2001.
[12] a) T. Sandmeyer, Ber. Dtsch. Chem. Ges. 1884, 17, 2650; b) H. H.
Hodgson, Chem. Rev. 1947, 40, 251; c) C. Galli, Chem. Rev. 1988,
88, 765, and references therein.
[13] a) K. Ishihara, Y. Furuya, H. Yamamoto, Angew. Chem. 2002,
114, 3109; Angew. Chem. Int. Ed. 2002, 41, 2983; b) C. W. Kuo,
J. L. Zhu, J. D. Wu, C. M. Chu, C. F. Yao, K. S. Shia, Chem.
Commun. 2007, 301; c) E. Choi, C. Lee, Y. Na, S. Chang, Org.
Lett. 2002, 4, 2369; d) K. Yamaguchi, H. Fujiwara, Y. Ogasawara,
M. Kotani, N. Mizuno, Angew. Chem. 2007, 119, 3996; Angew.
Chem. Int. Ed. 2007, 46, 3922; e) T. Oishi, K. Yamaguchi, N.
Mizuno, Angew. Chem. 2009, 121, 6404; Angew. Chem. Int. Ed.
2009, 48, 6286.
[14] a) W. Zhou, L. Zhang, N. Jiao, Angew. Chem. 2009, 121, 7228;
Angew. Chem. Int. Ed. 2009, 48, 7094; b) W. Zhou, J. Xu, L.
Zhang, N. Jiao, Org. Lett. 2010, 12, 2888; c) C. Qin, N. Jiao, J.
Am. Chem. Soc. 2010, 132, 15893; d) M. Lamani, K. R. Prabhu,
[18] For selected examples from our group, see: a) F. Chen, C. Qin, Y.
Cui, N. Jiao, Angew. Chem. 2011, 123, 11689; Angew. Chem. Int.
Ed. 2011, 50, 11487; b) C. Qin, T. Shen, C. Tang, N. Jiao, Angew.
Chem. 2012, 124, 7077; Angew. Chem. Int. Ed. 2012, 51, 6971; see
also Refs [14a] and [14c].
[19] For a leading review, see: A. Fꢀrstner, P. W. Davies, Angew.
Chem. 2007, 119, 3478; Angew. Chem. Int. Ed. 2007, 46, 3410;
and references therein.
[20] F. Chen, T. Shen, Y. Cui, N. Jiao, Org. Lett. 2012, 14, 4926.
[21] P. K. Kadaba, Synlett 1990, 349.
[22] a) A. Kumar, R. Narayanan, H. Shechter, J. Org. Chem. 1996, 61,
4462; b) P. A. Wender, J. M. Schaus, A. W. White, J. Am. Chem.
Soc. 1980, 102, 6159.
4
www.angewandte.org
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2013, 52, 1 – 5
These are not the final page numbers!

Angewandte
Chemie
Communications
Carbon–Carbon Bond Cleavage
T. Shen, T. Wang, C. Qin,
Three in one blow! A novel direct trans-
formation of alkynes into nitriles by
a silver-catalyzed nitrogenation reaction
ꢀ
N. Jiao*
&&&& — &&&&
through C C bond cleavage has been
developed. This research provides both
a new application for alkynes in organic
synthesis, and valuable mechanistic
insights into nitrogenation chemistry.
Silver-Catalyzed Nitrogenation of
Alkynes: A Direct Approach to Nitriles
through C C Bond Cleavage
ꢀ
Angew. Chem. Int. Ed. 2013, 52, 1 – 5
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!