钯催化的磺酰氯与有机锡烷的施蒂勒交叉偶联反应。

Palladium-catalyzed Stille cross-couplings of sulfonyl chlorides and organostannanes.

作者信息

Dubbaka Srinivas Reddy, Vogel Pierre

机构信息

Institute of Molecular and Biological Chemistry, Swiss Institute of Technology, BCH CH-1015 Lausanne, Switzerland.

出版信息

J Am Chem Soc. 2003 Dec 17;125(50):15292-3. doi: 10.1021/ja038328q.

DOI:10.1021/ja038328q

PMID:14664564

Abstract

Arene and phenylmethanesulfonyl chlorides can be cross-coupled with aryl, heteroaryl, and alkenylstannanes with desulfitation in the presence of 10 mol % CuBr.Me2S, 1.5 mol % Pd2dba3, and 5 mol % tri-2-furylphosphine in tetrahydrofuran or toluene under reflux. This extension of the Stille cross-coupling reaction realizes a new and economical method for the generation of C-C bonds. The palladium-catalyzed carbonylative Stille cross-coupling reactions of arenesulfonyl chlorides and organostannanes in the presence of CO (60 bar) at 110 degrees C in toluene generate the corresponding ketones. Arenesulfonyl chlorides are more reactive than aryl chlorides and aryl bromides in their Stille cross-coupling with organostannanes but less reactive than aryl iodides. The new methods disclosed for the generation of C-C bonds open new possibilities for medicinal chemistry and material sciences.

摘要

芳烃和苯甲磺酰氯可以在10 mol% CuBr·Me₂S、1.5 mol% Pd₂dba₃和5 mol% 三-2-呋喃基膦存在下，于四氢呋喃或甲苯中回流，与芳基、杂芳基和烯基锡烷进行交叉偶联并脱硫。这种对Stille交叉偶联反应的扩展实现了一种生成碳-碳键的新的经济方法。在110℃、60巴一氧化碳存在下，甲苯中钯催化的芳磺酰氯与有机锡烷的羰基化Stille交叉偶联反应生成相应的酮。芳磺酰氯在与有机锡烷的Stille交叉偶联反应中比芳基氯和芳基溴更具反应性，但比芳基碘的反应性低。所公开的生成碳-碳键的新方法为药物化学和材料科学开辟了新的可能性。