（+）-Jungermatrobrunin A 的对映选择性全合成。

Enantioselective Total Synthesis of (+)-Jungermatrobrunin A.

机构信息

School of Pharmaceutical Science and Technology, Tianjin University, Tianjin, 300072, China.

Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Department of Chemical Biology, College of Chemistry and Molecular Engineering, Synthetic and Functional Biomolecules Center and Peking-Tsinghua Center for Life Sciences, Peking University, Beijing, 100871, China.

出版信息

Angew Chem Int Ed Engl. 2019 Aug 5;58(32):10879-10883. doi: 10.1002/anie.201903682. Epub 2019 Jul 3.

DOI:10.1002/anie.201903682

PMID:31056826

Abstract

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 (-)-1α,6α-diacetoxyjungermannenone C (2). Along the way, a UV-light-induced bicyclo[3.2.1]octene ring rearrangement afforded (+)-12-hydroxy-1α,6α-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.

摘要

（+）-jungermatrobrunin A（1）的简洁和对映选择性全合成，其特征在于具有独特的双环[3.2.1]辛烯骨架和前所未有的过氧化物桥，通过利用（-）-1α，6α-二乙酰氧基jungermannenone C（2）的晚期可见光介导 Schenck 烯反应，以 13 步完成。一路上，UV 光诱导的双环[3.2.1]辛烯环重排提供了（+）-12-羟基-1α，6α-二乙酰氧基-ent-kaura-9（11），16-二烯-15-酮（4）。这些不同的光诱导骨架重排支持（+）-1、（-）-2 和（+）-4 之间可能存在生物发生关系。