Detailed mechanistic studies of several reactions catalyzed by diphenylprolinol ether catalysts led to the proposal that in many cases enantioselectivity is determined not in the stereogenic bond-forming step but is controlled by the relative stability and activity of diastereomeric intermediates downstream from this step in the catalytic cycle. Equilibration of intermediates prior to a definitive irreversible step combines kinetic and thermodynamic influences on ultimate product selectivity in a classic Curtin-Hammett scenario. Evidence is offered to suggest that this concept may represent a general phenomenon for pyrrolidine-based catalysts lacking an acidic directing proton. Implications for catalyst and reaction design are discussed.

<b>Award Address</b> (Gabor A. Somorjai Award for Creative Research in Catalysis sponsored by the Gabor A. and Judith K. Somorjai Endowment Fund). New paradigm for stereocontrol in organocatalysis

251st National Meeting (2016)

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Award Address (Gabor A. Somorjai Award for Creative Research in Catalysis sponsored by the Gabor A. and Judith K. Somorjai Endowment Fund). New paradigm for stereocontrol in organocatalysis