Open AccessEnantioselective Tail-to-Head Cyclizations Catalyzed by Dual-Hydrogen-Bond Donors
Author(s) -
Dennis A. Kutateladze,
Daniel A. Strassfeld,
Eric N. Jacobsen
Publication year - 2020
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.0c02665
Subject(s) - chemistry , enantioselective synthesis , catalysis , nucleophile , olefin fiber , substrate (aquarium) , hydrogen bond , transition state , molecule , combinatorial chemistry , stereochemistry , organic chemistry , oceanography , geology
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.