铜催化芳基溴化物的多米诺卤化物交换-氰化反应。

Copper-catalyzed domino halide exchange-cyanation of aryl bromides.

作者信息

Zanon Jacopo, Klapars Artis, Buchwald Stephen L

机构信息

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.

出版信息

J Am Chem Soc. 2003 Mar 12;125(10):2890-1. doi: 10.1021/ja0299708.

DOI:10.1021/ja0299708

PMID:12617652

Abstract

An efficient copper-catalyzed domino halogen exchange-cyanation procedure for aryl bromides was developed utilizing 10 mol % CuI, 20 mol % KI, 1.0 equiv of the inexpensive N,N'-dimethylethylenediamine as ligand, and 1.2 equiv of NaCN in toluene at 110 degrees C. The new method represents a significant improvement over the traditional Rosenmund-von Braun reaction: the reaction conditions are much milder, and the use of stoichiometric amounts of copper(I) cyanide and polar solvents is avoided; therefore the isolation and purification of the aromatic nitrile products is greatly simplified. In addition, the new method exhibits excellent functional group compatibility comparable to that of the analogous Pd-catalyzed cyanation methodology.

摘要

开发了一种高效的铜催化芳基溴化物多米诺卤交换-氰化反应方法，该方法使用10 mol%的碘化亚铜、20 mol%的碘化钾、1.0当量廉价的N,N'-二甲基乙二胺作为配体，以及1.2当量的氰化钠，在110℃的甲苯中进行反应。该新方法相对于传统的罗森蒙德-冯·布劳恩反应有显著改进：反应条件温和得多，避免了使用化学计量的氰化亚铜和极性溶剂；因此，大大简化了芳香腈产物的分离和纯化。此外，新方法表现出与类似的钯催化氰化方法相当的优异官能团兼容性。