Enantioselective Tail-to-Head Cyclizations Catalyzed by Dual-Hydrogen-Bond Donors

Chiral urea derivatives are shown to catalyze enantioselective tail-to-head cyclization reactions of neryl chloride analogues. Experimental data are consistent with a mechanism in which π-participation by the nucleophilic olefin facilitates chloride ionization and thereby circumvents simple eliminat...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2020-04, Vol.142 (15), p.6951-6956
Main Authors: Kutateladze, Dennis A, Strassfeld, Daniel A, Jacobsen, Eric N
Format: Article
Language:English
Subjects:
Catalysis
Cyclization
Humans
Hydrogen Bonding
Molecular Structure
Stereoisomerism
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Summary:Chiral urea derivatives are shown to catalyze enantioselective tail-to-head cyclization reactions of neryl chloride analogues. Experimental data are consistent with a mechanism in which π-participation by the nucleophilic olefin facilitates chloride ionization and thereby circumvents simple elimination pathways. Kinetic and computational studies support a cooperative mode of catalysis wherein two molecules of the urea catalyst engage the substrate and induce enantioselectivity through selective transition state stabilization.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.0c02665