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Total Syntheses of the Tetracyclic Cyclopiane Diterpenes Conidiogenone, Conidiogenol, and Conidiogenone B
Author(s) -
Hou SiHua,
Tu YongQiang,
Wang ShuangHu,
Xi ChaoChao,
Zhang FuMin,
Wang ShaoHua,
Li YanTao,
Liu Lin
Publication year - 2016
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.201600529
Subject(s) - regioselectivity , ring (chemistry) , stereochemistry , carbon atom , total synthesis , chemistry , quaternary carbon , absolute configuration , organic chemistry , enantioselective synthesis , catalysis
Abstract Total syntheses of the biologically important and structurally unique tetracyclic diterpenes conidiogenone, conidiogenol, and conidiogenone B of the cyclopiane class are reported. The absolute configuration of naturally occurring conidiogenone B was also corrected. The key step of our strategy involved the highly efficient construction of both ring C and the quaternary carbon center shared by rings A and C through a one‐step regioselective and diastereoselective cycloenlargement in the form of a semipinacol‐type rearrangement. In particular, the desired regioselectivity was made possible by properly adjusting the migratory aptitude of the migrating carbon atom through the introduction of an electron‐donating phenylthio group at this position.