季碳中心的不对称合成。（-）-马琳内酯的全合成。

Asymmetric synthesis of quaternary centers. Total synthesis of (-)-malyngolide.

作者信息

Trost B M, Tang W, Schulte J L

机构信息

Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.

出版信息

Org Lett. 2000 Dec 14;2(25):4013-5. doi: 10.1021/ol006599p.

DOI:10.1021/ol006599p

PMID:11112631

Abstract

[structure] The deracemization of 3-nonyl-3,4-epoxybut-1-ene with Pd(0) in the presence of chiral ligands using p-methoxybenzyl alcohol as a nucleophile proceeds regio- and enantioselectively to form the monoprotected vinylglycidol in 99% ee. This chiral building block was converted in seven steps to (-)-malyngolide, an antibiotic showing significant activity against Mycobacterium smegmatis and Streptococcus pyogenes. An interesting aspect involves controlling the diastereoselectivity of protonation of an enolate via a distal hydroxyl group.

摘要

[结构] 在对甲氧基苄醇作为亲核试剂存在的情况下，使用手性配体，Pd(0) 对 3-壬基-3,4-环氧丁-1-烯进行去消旋化反应，区域和对映选择性地生成对映体过量值为 99% 的单保护乙烯基缩水甘油。这个手性结构单元经七步反应转化为 (-)-马琳内酯，一种对耻垢分枝杆菌和化脓性链球菌具有显著活性的抗生素。一个有趣的方面涉及通过一个远端羟基来控制烯醇负离子质子化的非对映选择性。