F. Luo, C. Chu, Chien‐Hong Cheng
Feb 13, 1998
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Organometallics
Abstract
The palladium phosphine complexes Pd(PPh3)2Cl2/PPh3, Pd(PBu3)2Cl2, and Pd(dppp)2Cl2 (dppp = 1,2-bis(diphenylphosphino)propane) in the presence of zinc metal powder catalyze nitrile-group transfer from organic nitriles RCN (R = Me, Et, n-Pr, Bn, Ph) to bromoarenes to give the corresponding ArCN compounds. Only ortho-disubstituted bromoarenes (1-bromo-2-methylnaphthalene (1), 2-bromo-m-xylene, 2-bromomesitylene (3), 1-bromo-2-methoxynaphthalene, and 9-bromoanthracene) afforded good yields of the cyanation products. Analysis of the reaction mixture of 3 with benzyl cyanide using Pd(PBu3)2Cl2 as the catalyst showed the presence of dibenzyl ketone and a cyclic product, 2,4,6-tribenzyl-5-phenylpyrimidine, in addition to 2,4,6-trimethylbenzonitrile. To understand the mechanistic features of these catalytic reactions, a number of experiments were performed and the results are summarized as follows: (i) the palladium intermediate Pd(PPh3)2(2-Me-Np)Br (6; 2-Me-Np = 2-methylnaphthyl), which can be prepared separate...