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Enantioselective Total Synthesis of (+)‐Jungermatrobrunin A
Author(s) -
Wu Jinbao,
Kadonaga Yuichiro,
Hong Benke,
Wang Jin,
Lei Xiaoguang
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201903682
Subject(s) - enantioselective synthesis , bicyclic molecule , octene , chemistry , ring (chemistry) , stereochemistry , total synthesis , catalysis , organic chemistry , ethylene
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 .