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Total Synthesis of Aplydactone by a Conformationally Controlled C−H Functionalization
Author(s) -
Liu Chenguang,
Chen Renzhi,
Shen Yang,
Liang Zhanhao,
Hua Yuhui,
Zhang Yandong
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201703803
Subject(s) - stereocenter , chemistry , stereochemistry , total synthesis , ring (chemistry) , surface modification , enantioselective synthesis , organic chemistry , catalysis
A concise, protecting‐group‐free total synthesis of the unusual brominated sesquiterpene aplydactone is described. Our synthesis features a [2+2] photocycloaddition, a Wolff ring contraction, an unusual remote C−H functionalization to establish the highly strained tetracyclic core, and a hydrogen‐atom transfer (HAT) reaction to access the bromine‐containing stereocenter. A finely tuned conformation of the α‐diazoketone precursor is the key for the success of the late‐stage transannular C−H insertion to deliver a bridged six‐membered ring and a quaternary stereocenter (C6) between two quaternary carbon atoms (C1 and C7).