邻异丙烯基苯酚的催化不对称环羰基化反应：六元环内酯的对映选择性合成

Catalytic asymmetric cyclocarbonylation of o-isopropenylphenols: enantioselective synthesis of six-membered ring lactones.

作者信息

Dong Chune, Alper Howard

机构信息

Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario, Canada K1N 6N5.

出版信息

J Org Chem. 2004 Jul 23;69(15):5011-4. doi: 10.1021/jo040109f.

DOI:10.1021/jo040109f

PMID:15255729

Abstract

Cyclocarbonylation of o-isopropenylphenols with CO (500 psi) and H(2) (100 psi), using Pd(OAc)(2) and (+)-DIOP as the chiral catalyst, in CH(2)Cl(2) affords 3,4-dihydro-4-methylcoumarins in 60-85% yield and in up to 90% enantiomeric excess. The stereoselectivity is influenced by the structure of the chiral phosphine ligands and substrates, as well as by the reaction conditions.

摘要

以Pd(OAc)₂和(+)-DIOP作为手性催化剂，在二氯甲烷中，邻异丙烯基苯酚与一氧化碳（500 psi）和氢气（100 psi）进行环羰基化反应，可得到产率为60 - 85%、对映体过量高达90%的3,4 - 二氢 - 4 - 甲基香豆素。立体选择性受手性膦配体和底物的结构以及反应条件的影响。