Asymmetric Total Synthesis of Dankasterones A and B and Periconiastone A Through Radical Cyclization

被引：36

作者：

Chen, Pengquan ^{[1
]}

Wang, Cheng ^{[1
]}

Yang, Rui ^{[1
]}

Xu, Hongjin ^{[1
]}

Wu, Jinghua ^{[1
]}

Jiang, Huanfeng ^{[1
]}

Chen, Kai ^{[2
,3
]}

Ma, Zhiqiang ^{[1
]}

机构：

[1] South China Univ Technol, Sch Chem & Chem Engn, Key Lab Funct Mol Engn Guangdong Prov, Wushan Rd 381, Guangzhou 510641, Peoples R China

[2] Cent South Univ, Coll Chem & Chem Engn, Changsha 410083, Peoples R China

[3] Peking Univ, Lab Computat Chem & Drug Design, State Key Lab Chem Oncogen, Shenzhen Grad Sch, Shenzhen 518055, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2021年 / 60卷 / 10期

基金：

中国国家自然科学基金;

关键词：

cis-decalin; hydrogen atom transfer; radical cyclization; steroids; total synthesis; BEI TERPENOIDEN POLYENVERBINDUNGEN; BIOMIMETIC TOTAL-SYNTHESIS; NATURAL-PRODUCTS; UNACTIVATED OLEFINS; STEREOCHEMISTRY; HYDROAMINATION; HYDROGENATION; MITTEILUNG; REDUCTION; OXIDATION;

D O I：

10.1002/anie.202013881

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We describe herein the assembly of the cis-decalin framework through radical cyclization initiated by metal-catalyzed hydrogen atom transfer (MHAT), further applied it in the asymmetric synthesis of dankasterones A and B and periconiastone A. Position-selective C-H oxygenation allowed for installation of the necessary functionality. A radical rearrangement was adopted to create 13(14 -> 8)abeo-8-ergostane skeleton. Interconversion of dankasterone B and periconiastone A was realized through biomimetic intramolecular aldol and retro-aldol reactions. The MHAT-based approach, serves as a new dissection means, is complementary to the conventional ways to establish cis-decalin framework.

引用

页码：5512 / 5518

页数：7

共 99 条

[1] Dankasterone, a new class of cytotoxic steroid produced by a Gymnascella species from a marine sponge [J].