Title

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.

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