1 research outputs found
Construction of Stereogenic α,α-Disubstituted Cycloalkanones via 1° Amine Thiourea Dual Catalysis: Experimental Scope and Computational Analyses
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 organocatalyst scaffold
that are critical for stereoselectivity