pubs.acs.org/joc
Chelation-Assisted Palladium-Catalyzed Cascade Bromination/
Cyanation Reaction of 2-Arylpyridine and 1-Arylpyrazole C-H Bonds
Xiaofei Jia,† Dongpeng Yang,† Wenhui Wang,† Fang Luo,† and Jiang Cheng*,†,‡
†College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325027, P. R. China, and
‡State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, P. R. China
Received October 10, 2009
A chelation-assisted palladium-catalyzed cascade bromination/cyanation reaction of 2-arylpyridine
and 1-arylpyrazole C-H bonds has been developed. Notably, the reaction employs K3[Fe(CN)6] as a
safe and nontoxic cyanide source, providing aromatic nitriles in moderate to good yields in one-pot.
The procedure tolerates methoxy, chloro, fluoro, cyano, trifluoromethyl, and carbomethoxy groups.
Introduction
they represent versatile intermediates for further transfor-
mations in synthetic organic chemistry.2 The Rosenmund-
von Braun reaction3 (reaction of aryl halides with copper(I)
cyanide) and the Sandmeyer reaction4 (reaction of diazo-
nium salts with copper(I) cyanide) are widely used in the
preparation of benzonitriles. Compared to the classic meth-
ods, transition-metal-catalyzed cyanation of aryl halides is a
mild and direct method to access benzonitriles.5-7 However,
prefunctionalization was required to achieve benzonitriles.
Thus, development of a simple method is a highly desired
goal in synthetic chemistry.
Benzonitriles are of considerable interest in organic chem-
istry as integral ingredients of dyes, herbicides, natural
products, agrochemicals, and pharmaceuticals.1 In addition,
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Published on Web 11/25/2009
DOI: 10.1021/jo902185c
r
2009 American Chemical Society