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Enantioselective Approach to the Right‐Hand Substructure of Solanoeclepin A
Author(s) -
Lutteke Ginger,
Kleinnijenhuis Roel A.,
Beuving Remmelt J.,
de Gelder René,
Smits Jan M. M.,
van Maarseveen Jan H.,
Hiemstra Henk
Publication year - 2016
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201601094
Subject(s) - enantioselective synthesis , chemistry , cyclopropanation , moiety , allene , intramolecular force , ketone , butenolide , stereochemistry , transfer hydrogenation , total synthesis , allylic rearrangement , organic chemistry , catalysis , ruthenium
An enantioselective synthesis of the right‐hand substructure of solanoeclepin A has been developed. The key step was an intramolecular [2+2] photocycloaddition between an allene and a butenolide providing a methylenecyclobutane with three quaternary carbon atoms in a complex tetracyclic framework. Other crucial steps included an enantioselective Noyori transfer hydrogenation of a ketone, a diastereoselective silver‐mediated silyl dienolate allylation, and a diastereoselective cyclopropanation of an allylic alcohol. The installation of the bridgehead methyl group by reduction of the lactone moiety proved to be troublesome.