TY - JOUR
T1 - Carbonyl Activation in Electrophilic Polyene Cyclizations
T2 - A Toolbox for the Design of Isoprenoid Libraries
AU - Minassi, Alberto
AU - Pollastro, Federica
AU - Chianese, Giuseppina
AU - Caprioglio, Diego
AU - Taglialatela-Scafati, Orazio
AU - Appendino, Giovanni
N1 - Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/6/26
Y1 - 2017/6/26
N2 - 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.
AB - 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.
KW - biogenesis
KW - cyclization
KW - isoprenoids
KW - natural products
KW - reaction mechanisms
UR - http://www.scopus.com/inward/record.url?scp=85020178107&partnerID=8YFLogxK
U2 - 10.1002/anie.201703455
DO - 10.1002/anie.201703455
M3 - Article
SN - 1433-7851
VL - 56
SP - 7935
EP - 7938
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 27
ER -