Construction of Stereogenic α,α-Disubstituted Cycloalkanones via 1° Amine Thiourea Dual Catalysis: Experimental Scope and Computational Analyses.
Document Type
Article
Publication Date
4-20-2016
Publication Title
The Journal of Organic Chemistry
Volume
81
Issue
9
First page number:
3629
Last page number:
3637
Abstract
The mechanistic exploration and an expanded experimental discussion of the organocatalyzed, asymmetric Pfau–d’Angelo reaction by exploiting a bifunctional 1° amine thiourea catalyst system is disclosed. Notable breadth in substrate scope has been demonstrated on both the cyclic ketone moiety and the α,β-unsaturated electrophile. Exploration into the matched and mismatched selectivity of this process with a ketone containing pre-existing stereocenters has been demonstrated. Computational analyses of the reaction mechanism are reported. In concert with kinetic isotope effect (KIE) experiments, these computational results provide a detailed understanding of the likely mechanism, including the aspects of the organ catalyst scaffold that are critical for stereo selectivity.
Repository Citation
Kang, J. Y.,
Johnston, R. C.,
Snyder, K. M.,
Cheong, P. H.,
Carter, R. G.
(2016).
Construction of Stereogenic α,α-Disubstituted Cycloalkanones via 1° Amine Thiourea Dual Catalysis: Experimental Scope and Computational Analyses..
The Journal of Organic Chemistry, 81(9),
3629-3637.
http://dx.doi.org/10.1021/acs.joc.6b00280