Stereoselective synthesis of (E)-cinnamonitriles via heck arylation of acrylonitrile and aryl iodides in water

Article abstract of DOI:10.1081/SCC-120014770

Heck arylation of acrylonitrile and aryl iodides were carried out in the presence of catalytic amounts of Pd(OAc)₂ and Bu₄NBr in neat water and a variety of substituted (E)-cinnamonitriles were obtained in good yields under mild cond

Full text of DOI:10.1081/SCC-120014770

This article was downloaded by: [George Mason University]
On: 27 December 2014, At: 15:10
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK
Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic
Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsyc20
STEREOSELECTIVE SYNTHESIS OF (E)-CINNAMONITRILES
VIA HECK ARYLATION OF ACRYLONITRILE AND ARYL
IODIDES IN WATER
a
b
a
Hong Zhao , Ming-Zhong Cai & Chun-Yun Peng
a
Department of Chemistry , Jiangxi Normal University , Nanchang, 330027, P.R. China
b
Department of Chemistry , Jiangxi Normal University , Nanchang, 330027, P.R. China
Published online: 22 May 2009.
To cite this article: Hong Zhao , Ming-Zhong Cai & Chun-Yun Peng (2002) STEREOSELECTIVE SYNTHESIS OF (E)-
CINNAMONITRILES VIA HECK ARYLATION OF ACRYLONITRILE AND ARYL IODIDES IN WATER, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:22, 3419-3423, DOI: 10.1081/
SCC-120014770
To link to this article: http://dx.doi.org/10.1081/SCC-120014770
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
SYNTHETIC COMMUNICATIONS
Vol. 32, No. 22, pp. 3419–3423, 2002
STEREOSELECTIVE SYNTHESIS OF
(E)-CINNAMONITRILES VIA HECK
ARYLATION OF ACRYLONITRILE AND
ARYL IODIDES IN WATER
Hong Zhao, Ming-Zhong Cai,* and Chun-Yun Peng
Department of Chemistry, Jiangxi Normal University,
Nanchang 330027, P.R. China
ABSTRACT
Heck arylation of acrylonitrile and aryl iodides were carried
out in the presence of catalytic amounts of Pd(OAc)2
and Bu NBr in neat water and a variety of substituted
4
(E)-cinnamonitriles were obtained in good yields under mild
conditions.
Key Words: Stereoselective synthesis; Heck arylation; (E)-
Cinnamonitrile
Cinnamonitriles are important synthetic intermediates and usually
prepared by following methods, such as the reaction of cinnamaldehyde
[
1]
and dimethylsulfur diimide,
the reaction of the thallium reagent
[2]
ArTl(O CCCl ) ,
2
Wittig-Horner reaction of (EtO) POCH CN with
2 2
and the treatment of acid chloride with sulfonamide.
3 2
[3]
[4]
aldehyde
*
Corresponding author. E-mail: caimz@Fm365.com
419
3
DOI: 10.1081/SCC-120014770
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
3
420
ZHAO, CAI, AND PENG
In recent years, more attention has been given to the stereoselective syn-
[
5]
thesis of (E) and (Z)-cinnamonitriles. Huang et al. reported that (Z)-
cinnamonitriles were prepared in 78–98% yield by the desulfonylation of
a-phenylsulfonylcinnamonitriles in the presence of NaHTe. Guo and
[6]
Zhang found that (E)-cinnamonitriles could be obtained in 68–85%
yield by a procedure of reduction of a-phenylsulfonylcinnamonitriles with
SmI2 in THF-MeOH solution. Although these methods have provided
simple routes for stereoselective synthesis of (E) and (Z)-cinnamonitriles,
sometimes the a-phenylsulfonylcinnamonitriles are not readily available.
A convenient alternative technical synthesis of (E)-cinnamonitriles is the
Heck arylation of aryl iodides and acrylonitrile, the arylation reaction is
[
7–8]
carried out in anhydrous organic solvent.
medium for transition metal catalyzed reactions is very attractive for
The use of water as a reaction
[9,10]
organic synthesis,
palladium-catalyzed arylation reactions of styrene, methyl acrylate and
for both economic and safety reasons. Recently, the
[
11,12]
acrylic acid in neat water were reported.
To our knowledge, no Heck
arylation of acrylonitrile with aryl iodides in water has been reported. In this
paper, we wish to report Heck arylation of acrylonitrile with various aryl
iodides in the presence of catalytic amounts of Pd(OAc) and Bu NBr in
2
4
neat water without any organic co-solvents (Sch. 1).
Treatment of iodobenzene (1 mmol) with acrylonitrile (4 mmol) in
ꢀ
pure water (3 mL) at 80–90 C for 10 h in the presence of Pd(OAc)
0.05 mmol), Bu NBr (0.1 mmol) and NaHCO3 (2 mmol) afforded
2
(
4
(
E)-cinnamonitrile in 81% yield. We applied the reaction to various sub-
stituted iodobenzenes, typical results are summarized in Table 1. As seen
from the Table 1, the arylation of acrylonitrile with substituted iodo-
benzenes in neat water also proceeded smoothly and a variety of substituted
(
E)-cinnamonitriles were obtained in good yields. The arylation reaction can
tolerate a variety of functional groups on the aryl iodides, both strongly
electron donating and withdrawing substituents can be present. The reac-
tivity of iodobenzene with electron withdrawing substituent is higher than
that of iodobenzene with electron donating substituent. All products gave
1
satisfactory m.p., IRand H NMRspectra.
In conclusion, with its stereoselectivity, mild reaction condition, as
well as simple operation, the palladium-catalyzed arylation of acrylonitrile
Scheme 1.

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
SYNTHESIS OF (E)-CINNAMONITRILES
3421

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
3
422
ZHAO, CAI, AND PENG
with aryl iodides in neat water provides a practical procedure for the
stereoselective synthesis of (E)-cinnamonitriles.
EXPERIMENTAL
Mps were taken with a Yanoco micro melting pointing apparatus and
are uncorrected. IRspectra were recorded on a Shimadzu I R- 435 instru-
1
ment. H NMRspectra were obtained with a JEOL FX-90Q(90 MHz)
spectrometer using Me Si as an internal standard in CDCl as solvent.
4
3
Acrylonitrile was distilled prior to use. Other reagents were used as received
without further purification.
Typical Procedure for the Synthesis of (E)-Cinnamonitrile
A mixture of iodobenzene (1 mmol), acrylonitrile (4 mmol), Pd(OAc)2
0.05 mmol), Bu NBr (0.1 mmol) and NaHCO (2 mmol) in distilled water
4 3
(
ꢀ
(
3 mL) was stirred vigorously under nitrogen at 80–90 C for 10 h. The reac-
tion mixture was cooled and extracted with diethyl ether (3 ꢁ 20 mL). The
ethereal solution was washed with distilled water (3 ꢁ 20 mL), then dried
over anhydrous sodium sulfate. After evaporating the solvent under reduced
pressure, the residue was purified by preparative TLC on silica gel (light
petroleum : ethyl acetate ¼ 9 : 1) to afford (E)-cinnamonitrile (0.105 g, 81%).
REFERENCES
1
2
. Georg, G.I.; Pfeifer, S.A. Tetrahedron Lett. 1985, 26, 2739.
. Sakae, U.; Haruo, M.; Mikio, W.; Masaya, O.; Osamu, I.; Takaaki, I.;
Katsuhiko, I. Bull. Chem. Soc. Jpn. 1980, 52, 553.
3
4
5
. Francoise, T.B.; Andre, F. Synthesis 1979, 884.
. Hulkenberg, A.; Troost, J.J. Tetrahedron Lett. 1982, 23, 1505.
. Huang, X.; Pi, J.H.; Huang, Z.Z. Phosphorus Sulfur Silicon Relat.
Elem. 1992, 67, 177.
6
7
8
9
. Guo, H.; Zhang, Y. J. Chem. Res. 1999, 342.
. Ziegler, C.B.; Heck, R.F. J. Org. Chem. 1978, 43, 2941.
. Heck, R.F. Acc. Chem. Res. 1979, 12, 146.
. Cazalnuovo, A.L.; Calabreze, J.C. J. Am. Chem. Soc. 1990, 112, 4324.
1
1
0. Wallow, T.I.; Novak, B.M. J. Am. Chem. Soc. 1991, 113, 7411.
1. Bumagin, N.A.; Bykov, V.V.; Sukhomlinova, L.I.; Tolstaya, T.P.;
Beletskaya, I.P. J. Organomet. Chem. 1995, 486, 259.

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
SYNTHESIS OF (E)-CINNAMONITRILES
3423
12. Jeffery, T. Tetrahedron Lett. 1994, 35, 3051.
13. Pastushak, N.O.; Stadniichuk, N.F.; Dombrovskii, A.V. Zh. Ohshch.
Khim. 1963, 33, 2950.
Received in the Netherlands November 11, 2001

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.