Open AccessBiomimetic 2-Imino-Nazarov Cyclizations via Eneallene Aziridination
Author(s) -
Joshua R. Corbin,
Devin R. Ketelboeter,
Israel Fernández,
Jennifer M. Schomaker
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.0c02441
Subject(s) - chemistry , nitrene , bicyclic molecule , stereocenter , synthon , vicinal , alkene , lewis acids and bases , reactivity (psychology) , combinatorial chemistry , organocatalysis , stereochemistry , catalysis , amine gas treating , ring (chemistry) , enantioselective synthesis , organic chemistry , medicine , alternative medicine , pathology
Amidoallyl cations are appealing three-carbon synthons for the preparation of complex amine-containing carbocycles; however, methods to generate and utilize these reactive species are limited and underexplored compared to those for oxallyl cations. Here we disclose a bioinspired strain-driven ring opening of bicyclic methyleneaziridines to 2-amidopentadienyl cation intermediates that readily engage in Nazarov cyclizations. Advantages of this strategy include ease of generation and improved reactivity compared to 3-pentadienyl cations, control over the ultimate position of the alkene, the potential for high dr between vicinal stereocenters, and the ability to further elaborate the products to fully substituted aminocyclopentanes. Experimental and computational studies support a dual role for the Rh 2 L n complex as both a nitrene transfer catalyst and a Lewis acid promoter, insight that provides a framework for the future development of asymmetric 2-imino-Nazarov cyclizations.