使用（-）-鹰爪豆碱对映选择性钯（II）催化的需氧醇氧化反应的范围

Scope of enantioselective palladium(II)-catalyzed aerobic alcohol oxidations with (-)-sparteine.

作者信息

Mandal Sunil K, Jensen David R, Pugsley Jacob S, Sigman Matthew S

机构信息

Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City 84112, USA.

出版信息

J Org Chem. 2003 May 30;68(11):4600-3. doi: 10.1021/jo0269161.

DOI:10.1021/jo0269161

PMID:12762783

Abstract

Evaluation of the substrate scope for Pd(II)/ (-)-sparteine catalyzed aerobic oxidative kinetic resolution of secondary alcohols is disclosed. An improved system is found with use of tert-butyl alcohol solvent in which benzylic and aliphatic alcohols as well as alcohols containing olefins are effectively oxidatively resolved. For substrates that successfully undergo oxidative kinetic resolution, k(rel) values are generally between 10 and 20. Successful scale-up of various substrates to 10-mmol scale is described. Extension to oxidative desymmetrization of 1,3-meso-diols is successful with enantiomeric excesses ranging from 78 to 85%.

摘要

本文报道了对钯（II）/（-）-鹰爪豆碱催化仲醇有氧氧化动力学拆分反应底物范围的评估。研究发现，使用叔丁醇作为溶剂可改进反应体系，在此体系中，苄醇、脂肪醇以及含烯烃的醇类均可有效实现氧化拆分。对于成功进行氧化动力学拆分的底物，k（rel）值通常在10至20之间。文中描述了将各种底物成功放大至10 mmol规模的过程。将该反应扩展至1,3-内消旋二醇的氧化去对称化反应也取得了成功，对映体过量率在78%至85%之间。