通过呋甾烷-26-酸的级联环开关过程立体选择性合成(-)-长春碱及其同系物。

Stereoselective Synthesis of (-)-Verazine and Congeners via a Cascade Ring-Switching Process of Furostan-26-acid.

机构信息

Engineering Center of Catalysis and Synthesis for Chiral Molecules, Fudan University, Shanghai 200433, China.

Shanghai Engineering Center of Industrial Asymmetric Catalysis for Chiral Drugs, Shanghai 200433, China.

出版信息

Org Lett. 2020 Apr 3;22(7):2761-2765. doi: 10.1021/acs.orglett.0c00747. Epub 2020 Mar 23.

DOI:10.1021/acs.orglett.0c00747

PMID:32202118

Abstract

An efficient synthetic strategy for three natural -type cholestane alkaloids isolated from the plants, based on commercially available naturally occurring and abundant (-)-diosgenin (), as exemplified in the concise asymmetric synthesis of (-)-verazine (), (-)-veramiline () (proposed structure), and its 22-epimer, (-)-oblonginine (), is presented. This work highlights the application of a cascade ring-switching process of (-)-diosgenin to achieve the E-ring opening and construction of chiral six-membered lactone challenges in -type cholestane alkaloid synthesis. This approach enables the synthesis of related natural and nature-like novel cholestane alkaloids, opening up opportunities for more extensive exploration of cholestane alkaloid biology.

摘要

本文提出了一种从植物中分离得到的三种天然型胆甾烷生物碱的高效合成策略，该策略以商业可得的天然且丰富的薯蓣皂苷元（()-Diosgenin ()）为基础，如简洁不对称合成 (-)-verazine ()、(-)-veramiline ()（提议结构）及其 22-差向异构体 (-)-oblonginine ()所示。这项工作强调了 (-)-薯蓣皂苷元的级联环开关过程在实现 E 环开环和构建手性六元内酯挑战方面在 -型胆甾烷生物碱合成中的应用。这种方法能够合成相关的天然和类天然新型胆甾烷生物碱，为更广泛地探索胆甾烷生物碱生物学开辟了道路。