Enantioselective Total Synthesis of (+)-Jungermatrobrunin A

被引：39

作者：

Wu, Jinbao ^{[1
,2
,3
]}

Kadonaga, Yuichiro ^{[2
,3
]}

Hong, Benke ^{[2
,3
]}

Wang, Jin ^{[2
,3
]}

Lei, Xiaoguang ^{[2
,3
]}

机构：

[1] Tianjin Univ, Sch Pharmaceut Sci & Technol, Tianjin 300072, Peoples R China

[2] Peking Univ, Key Lab Bioorgan Chem & Mol Engn, Beijing Natl Lab Mol Sci, Minist Educ,Dept Chem Biol,Coll Chem & Mol Engn,S, Beijing 100871, Peoples R China

[3] Peking Univ, Peking Tsinghua Ctr Life Sci, Beijing 100871, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 32期

基金：

中国国家自然科学基金;

关键词：

peroxide formation; photochemistry; radical cyclization; rearrangement; total synthesis; ENT-KAURANE DITERPENOIDS; 1ST TOTAL-SYNTHESIS; LUNGSHENGENIN-D; REARRANGEMENTS; CONSTRUCTION; CONVERSION; KETONES; ACID; BETA;

D O I：

10.1002/anie.201903682

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A concise and enantioselective total synthesis of (+)-jungermatrobrunin A (1), which features a unique bicyclo[3.2.1]octene ring skeleton with an unprecedented peroxide bridge, was accomplished in 13 steps by making use of a late-stage visible-light-mediated Schenck ene reaction of (-)-1 alpha,6 alpha-diacetoxyjungermannenone C (2). Along the way, a UV-light-induced bicyclo[3.2.1]octene ring rearrangement afforded (+)-12-hydroxy-1 alpha,6 alpha-diacetoxy-ent-kaura-9(11),16-dien-15-one (4). These divergent photo-induced skeletal rearrangements support a possible biogenetic relationship between (+)-1, (-)-2, and (+)-4.

引用

页码：10879 / 10883

页数：5

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