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Stereoselective Total Synthesis of Hetisine‐type C 20 ‐Diterpenoid Alkaloids: Spirasine IV and XI
Author(s) -
Zhang Quanzheng,
Zhang Zhongshan,
Huang Zhong,
Zhang Changhui,
Xi Song,
Zhang Min
Publication year - 2018
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.201711414
Subject(s) - intramolecular force , stereoselectivity , moiety , chemistry , regioselectivity , aldol reaction , stereochemistry , cycloaddition , bicyclic molecule , ring (chemistry) , octane , total synthesis , terpenoid , organic chemistry , catalysis
The first total synthesis of the architecturally complex hetisine‐type heptacyclic C 20 ‐diterpenoid alkaloids (±)‐spirasine IV and XI is reported. The A/F/G/C tetracyclic skeleton with the challenging N−C6 and C14−C20 linkages was efficiently constructed by an intramolecular azomethine‐ylide‐based 1,3‐dipolar cycloaddition with unusual regioselectivity. SmI 2 ‐mediated free‐radical addition to the arene moiety without prior dearomatization and a stereoselective intramolecular aldol reaction further enabled rapid access to the hetisine core, providing a bicyclo[2.2.2]octane ring with a new oxygen substitution pattern.