铜（I）盐介导的炔基硅烷的偶联反应：共轭二炔和二取代乙炔的新合成方法

Coupling Reactions of Alkynylsilanes Mediated by a Cu(I) Salt: Novel Syntheses of Conjugate Diynes and Disubstituted Ethynes.

作者信息

Nishihara Y, Ikegashira K, Hirabayashi K, Ando Ji, Mori A, Hiyama T

机构信息

Research Laboratory of Resources Utilization, Tokyo Institute of Technology, 4259 Nagatsuta, Yokohama 226-8503, Japan.

出版信息

J Org Chem. 2000 Mar 24;65(6):1780-1787. doi: 10.1021/jo991686k.

DOI:10.1021/jo991686k

PMID:10814151

Abstract

Reaction of 1-trimethylsilylalkyne with copper(I) chloride in a polar solvent, DMF, at 60 degrees C under an aerobic conditions smoothly undergoes homo-coupling to give the corresponding symmetrical 1,3-butadiynes in 70-99% yields. In addition, (arylethynyl)trimethylsilanes are found to couple with aryl triflates and chlorides in the presence of Cu(I)/Pd(0) (10 mol %/5 or 10 mol %) cocatalyst system to give the corresponding diarylethynes in 49-99% yields. The cross-coupling reaction is applied to a one-pot synthesis of the corresponding unsymmetrical diarylethynes from (trimethylsilyl)ethyne via sequential Sonogashira-Hagihara and the present cross-coupling reactions using two different aryl triflates. The reactions of (arylethynyl)trimethylsilanes with aryl(chloro)ethynes in the presence of 10 mol % of CuCl also yield the corresponding unsymmetrical 1,3-butadiynes in 43-97% yields.

摘要

在有氧条件下，于60℃在极性溶剂N,N - 二甲基甲酰胺（DMF）中，1 - 三甲基硅基炔与氯化亚铜发生反应，顺利地进行均偶联反应，以70 - 99%的产率得到相应的对称1,3 - 丁二炔。此外，发现在Cu(I)/Pd(0)（10 mol%/5或10 mol%）共催化剂体系存在下，（芳基乙炔基）三甲基硅烷能与芳基三氟甲磺酸酯和氯化物发生偶联反应，以49 - 99%的产率得到相应的二芳基乙炔。该交叉偶联反应应用于从（三甲基硅基）乙炔通过连续的Sonogashira - Hagihara反应和使用两种不同芳基三氟甲磺酸酯的本交叉偶联反应一锅法合成相应的不对称二芳基乙炔。在10 mol%的氯化亚铜存在下，（芳基乙炔基）三甲基硅烷与芳基（氯）乙炔的反应也能以43 - 97%的产率得到相应的不对称1,3 - 丁二炔。