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Total Synthesis of the Diterpene Waihoensene
Author(s) -
Rosenbaum LisaCatherine,
Häfner Maximilian,
Gaich Tanja
Publication year - 2021
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.202011298
Subject(s) - stereocenter , enantioselective synthesis , total synthesis , diterpene , stereochemistry , intramolecular force , chemistry , natural product , alkylation , catalysis , organic chemistry
A racemic and scalable enantioselective total synthesis of (+)‐waihoensene was accomplished. (+)‐Waihoensene belongs to the diterpene natural product family, and it features an angular triquinane substructure motif. Its tetracyclic [6.5.5.5]backbone is all‐ cis ‐fused, containing six contiguous stereocenters, four of which are quaternary. These structural features were efficiently installed by means of a diastereoselective radical cyclization, followed by an intramolecular Pauson–Khand reaction, a diastereoselective α‐alkylation, and a diastereoselective 1,4‐addition reaction. Enantioselectivity was introduced at an early stage, by an asymmetric palladium catalyzed decarboxylative allylation reaction on gram scale.