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Mechanistic Dichotomy: Cu(II)- and Enzyme-Catalyzed Aldol Reaction
K. C. Fortner, M. D. Shair*
Harvard University, Cambridge, USA
24 April 2007 (online)
This is a nice mechanistic follow-up comparing the Shair group’s previously reported catalytic asymmetric thioester aldol reaction to the enzymatic mechanism (M. Shair and co-workers J. Am. Chem. Soc. 2005, 127, 7284-7285). Kinetics, kinetic isotope effects (both deuterium and 13C), and crossover experiments were performed and it was concluded that the two systems react under distinct mechanisms. The Cu(II)-catalyzed reaction undergoes the aldol reaction followed by decarboxylation while the enzymatic version undergoes decarboxylation to form the enolate, which then acts in the aldol reaction.