（Z）-二取代烯丙醇的直接、立体专一性生成。

Direct, stereospecific generation of (Z)-disubstituted allylic alcohols.

作者信息

Jeon Sang-Jin, Fisher Ethan L, Carroll Patrick J, Walsh Patrick J

机构信息

P. Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.

出版信息

J Am Chem Soc. 2006 Aug 2;128(30):9618-9. doi: 10.1021/ja061973n.

DOI:10.1021/ja061973n

PMID:16866501

Abstract

A one-pot method to prepare highly functionalized (Z)-disubstituted allylic alcohols is introduced. Hydroboration of a variety of 1-bromo-1-acetylenes with dicyclohexyl borane, reaction with t-BuLi, and transmetalation to zinc generates a (Z)-disubstituted vinylzinc reagent. In situ reaction of this reagent with aldehydes generates (Z)-disubstituted allylic alcohols in high yields (81-97%). Addition to chiral protected alpha- or beta-oxygenated aldehydes proceeds with diastereoselectivities between 6:1 and 18:1. The anti-Felkin product is obtained in most cases.

摘要

介绍了一种制备高官能化（Z）-二取代烯丙醇的一锅法。各种1-溴-1-乙炔与二环己基硼烷进行硼氢化反应，与叔丁基锂反应，再与锌进行转金属化反应，生成（Z）-二取代乙烯基锌试剂。该试剂与醛原位反应可高产率（81-97%）生成（Z）-二取代烯丙醇。加成到手性保护的α-或β-氧化醛时，非对映选择性为6:1至18:1。在大多数情况下得到反式费尔金产物。