钯催化环己二烯酮的反应：由炔烃乙酰氧基化引发的区域选择性环化反应

Palladium-catalyzed reactions of cyclohexadienones: regioselective cyclizations triggered by alkyne acetoxylation.

作者信息

Tello-Aburto Rodolfo, Harned Andrew M

机构信息

Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA.

出版信息

Org Lett. 2009 Sep 3;11(17):3998-4000. doi: 10.1021/ol901642w.

DOI:10.1021/ol901642w

PMID:19708708

Abstract

Regioselective cyclizations of alkyne-tethered cyclohexadienones can be accomplished under palladium catalysis. The cyclization involves an initial Pd-mediated acetoxylation of the alkyne, followed by migratory insertion and protonolysis of the resulting palladium enolate. The predictable regioselectivity of these atom-economical and stereoselective reactions is influenced by developing steric interactions during migratory insertion of a vinyl palladium intermediate.

摘要

在钯催化下，炔基连接的环己二烯酮的区域选择性环化反应能够实现。该环化反应首先是钯介导的炔烃的乙酰氧基化反应，接着是迁移插入反应以及所得钯烯醇盐的质子解反应。这些原子经济性和立体选择性反应可预测的区域选择性，受到乙烯基钯中间体迁移插入过程中逐渐形成的空间相互作用的影响。