Studies on the regioselectivity of the Baeyer-Villiger reaction of 3-keto steroids: Conformational effects determine the migration aptitude

被引：14

作者：

Rivera, Daniel G.

Pando, Orlando

Suardiaz, Reynier

Coll, Francisco

机构：

[1] Leibniz Inst Plant Biochem, Dept Bioorgan Chem, D-06120 Halle, Germany

[2] Univ Havana, Fac Chem, Ctr Nat Prod Study, Havana 10400, Cuba

[3] Univ Havana, Fac Chem, Dept Phys Chem, Havana 10400, Cuba

来源：

STEROIDS | 2007年 / 72卷 / 05期

关键词：

steroidal sapogenins; Baeyer-Villiger reaction; lactonization; bile acids;

D O I：

10.1016/j.steroids.2007.01.002

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

A detailed study of the Baeyer-Villiger reaction of 3-ketosteroids has been performed by using m-chloroperoxybenzoic and trifluoroperoxyacetic acids as oxidants. The process was fully regiospecific for 3-keto-5 alpha-steroids with the employ of both peracids, and only partially regioselective for 3-keto-5 beta-steroids by using trifluoroperoxyacetic acid. Interestingly, the reaction resulted completely unselective for 3-keto-5 beta-steroids by using m-chloroperoxybenzoic acid. Theoretical studies were performed to explain the regiochemistry of this process, which is suggested to be controlled by conformational effects in the transition state of the Criegee rearrangement. (c) 2007 Elsevier Inc. All rights reserved.

引用

页码：466 / 473

页数：8