Joseph A. Izzo, Yaroslaw Myshchuk, Jennifer S. Hirschi
Apr 17, 2019
Citations
1
Influential Citations
11
Citations
Journal
Organic & biomolecular chemistry
Abstract
The mechanism of the enantioselective Michael addition of diethyl malonate to trans-β-nitrostyrene catalyzed by a tertiary amine thiourea organocatalyst is explored using experimental 13C kinetic isotope effects and density functional theory calculations. Large primary 13C KIEs on the bond-forming carbon atoms of both reactants suggest that carbon-carbon bond formation is the rate-determining step in the catalytic cycle. This work resolves conflicting mechanistic pictures that have emerged from prior experimental and computational studies.