Premium
Asymmetric Nazarov Cyclizations of Unactivated Dienones by Hydrogen‐Bond‐Donor/Lewis Acid Co–Catalyzed, Enantioselective Proton‐Transfer
Author(s) -
Metternich Jan B.,
Reiterer Martin,
Jacobsen Eric N.
Publication year - 2020
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.202000831
Subject(s) - chemistry , enantioselective synthesis , catalysis , lewis acids and bases , hydrogen bond , silylation , proton , chiral lewis acid , combinatorial chemistry , medicinal chemistry , organic chemistry , stereochemistry , molecule , physics , quantum mechanics
We report an enantioselective Nazarov cyclization catalyzed by chiral hydrogen‐bond‐donors in concert with silyl Lewis acids. The developed transformation provides access to tri‐substituted cyclopentenones in high levels of enantioselectivity (up to 95% e.e.) from a variety of simple unactivated dienones. Kinetic and mechanistic studies are consistent with a reversible 4π‐electrocyclization C−C bond‐forming step followed by rate‐ and enantio‐determining proton‐transfer as the mode of catalysis.