Premium
Carbonyl Activation in Electrophilic Polyene Cyclizations: A Toolbox for the Design of Isoprenoid Libraries
Author(s) -
Minassi Alberto,
Pollastro Federica,
Chianese Giuseppina,
Caprioglio Diego,
TaglialatelaScafati Orazio,
Appendino Giovanni
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201703455
Subject(s) - polyene , electrophile , chemistry , lewis acids and bases , cationic polymerization , terpenoid , stereochemistry , chemical space , catalysis , organic chemistry , drug discovery , biochemistry
An approach to biogenetically overlooked areas of the isoprenoid chemical space is presented. This strategy is based on the generation of a cationic center in functionalized polyolefins by Lewis acid activation of a carbonyl group, rather than by electrophilic attack at a double bond. Starting from the monocyclic humulane trienone zerumbone, polycyclic sesquiterpenoid skeletons which are either not reported as natural products or biogenetically enigmatic in terms of the isoprenoid rule, were obtained by modulating the Lewis acid catalyst. In the course of these studies, the surprising formation of a strained E ‐cyclooctene motif was observed in a cyclization reaction.