Synfacts 2007(5): 0514-0514  
DOI: 10.1055/s-2007-968454
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Mechanistic Dichotomy: Cu(II)- and Enzyme-Catalyzed Aldol Reaction

Contributor(s): Hisashi Yamamoto, Matthew B. Boxer
K. C. Fortner, M. D. Shair*
Harvard University, Cambridge, USA
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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.