（+）-戈尼他二醇的全立体选择性合成。

Total stereoselective synthesis of (+)-goniothalesdiol.

作者信息

Carreño M Carmen, Hernández-Torres Gloria, Urbano Antonio, Colobert Françoise

机构信息

Departamento de Química Orgánica (C-I), Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid, Spain.

出版信息

Org Lett. 2005 Nov 24;7(24):5517-20. doi: 10.1021/ol0523603.

DOI:10.1021/ol0523603

PMID:16288545

Abstract

[reaction: see text] The stereoselective synthesis of (+)-goniothalesdiol (1) was accomplished in nine steps starting from commercially available (-)-(2S,3S)-dimethyl D-tartrate (3). The key features were a completely diastereoselective reduction of a beta-ketosulfoxide to generate the stereogenic center at C-5 in 7 and formation of the 2,5-cis-substituted tetrahydrofuran ring in 10 from a stereoselective Et(3)SiH/TMSOTf-promoted reductive cyclization/deoxygenation.

摘要

[反应：见正文] 从市售的（-）-（2S，3S）-二甲基 D-酒石酸酯（3）开始，通过九步反应完成了（+）-戈尼他二醇（1）的立体选择性合成。关键步骤包括β-酮亚砜的完全非对映选择性还原，以在7中C-5位生成手性中心，以及通过立体选择性的Et(3)SiH/TMSOTf促进的还原环化/脱氧反应，在10中形成2,5-顺式取代的四氢呋喃环。