可乐米肽的对映选择性全合成及其绝对构型的确定和结构修正。

Enantioselective total synthesis of colomitides and their absolute configuration determination and structural revision.

作者信息

Yang Hongguang, Liu Xiaoyu, Li Xiaoyu, Shi Xiang, Yang Feilong, Jiao Xiaozhen, Xie Ping

机构信息

State Key Laboratory of Bioactive Substances and Functions of Natural Medicines, Institute of Materia Medica, Beijing Key Laboratory of Active Substances Discovery and Druggability Evaluation, Peking Union Medical College and Chinese Academy of Medical Sciences, Beijing 100050, PR China.

出版信息

Org Biomol Chem. 2017 May 3;15(17):3728-3735. doi: 10.1039/c7ob00539c.

DOI:10.1039/c7ob00539c

PMID:28406516

Abstract

An efficient stereoselective synthetic approach to colomitides, 2,7-dioxabicyclo[3.2.1]octane-type natural products, is reported. Key steps are a stereocontrolled aldol reaction and a gold-catalyzed cycloisomerization. This synthetic strategy has been applied for the first asymmetric total synthesis of the proposed colomitides and their possible diastereomers. Comparison of their H and C NMR spectra and specific rotations with those of the natural product revealed that the structure of colomitide A should be revised to 1c, and that the absolute stereochemistries of colomitides A and B are 2'R,4R,5R,8S,1R and 2'R,4S,5R,8S,1R.

摘要

报道了一种高效立体选择性合成方法，用于制备2,7 - 二氧杂双环[3.2.1]辛烷型天然产物科洛米特（colomitides）。关键步骤是立体控制的羟醛反应和金催化的环异构化反应。该合成策略已应用于首次不对称全合成所提出的科洛米特及其可能的非对映异构体。将它们的氢谱和碳谱以及比旋光度与天然产物的进行比较，结果表明科洛米特A的结构应修正为1c，并且科洛米特A和B的绝对立体化学结构分别为2'R,4R,5R,8S,1R和2'R,4S,5R,8S,1R。