脱氧甜菜碱、甜菜碱及其4-差向异构体的非对映选择性合成。

Diastereoselective syntheses of deoxydysibetaine, dysibetaine, and its 4-epimer.

作者信息

Langlois Nicole, Le Nguyen Bao K

机构信息

Institut de Chimie des Substances Naturelles, CNRS, 91198 Gif-sur-Yvette, France.

出版信息

J Org Chem. 2004 Oct 29;69(22):7558-64. doi: 10.1021/jo040216+.

DOI:10.1021/jo040216+

PMID:15497982

Abstract

(+/-)-Deoxydysibetaine 2 and 4-epi-dysibetaine 3 were prepared in a few steps from methyl pyroglutamate through a regioselective Mannich reaction at C-2. Natural (2S,4S)-dysibetaine 1, a sponge metabolite isolated from Dysidea herbacea, and (2S)-2 were synthesized from enantiopure (S)-pyroglutaminol with very high stereoselectivity. The key steps were an original formation of stereogenic quaternary center C-2 and the diastereoselective hydroxylation at C-4.

摘要

（±）-脱氧甜菜碱2和4-表-甜菜碱3是由焦谷氨酸甲酯经几步反应通过在C-2位的区域选择性曼尼希反应制备而成。天然的（2S，4S）-甜菜碱1是从草本海绵（Dysidea herbacea）中分离得到的一种海绵代谢产物，（2S）-2由对映纯的（S）-焦谷氨醇以非常高的立体选择性合成。关键步骤是立体中心季碳C-2的原始形成以及C-4位的非对映选择性羟基化。