Please use this identifier to cite or link to this item: https://doi.org/10.1021/ja4005893
Title: Oxyanion hole stabilization by C-H·O Interaction in a transition state -a three-point interaction model for cinchona alkaloid-catalyzed asymmetric methanolysis of meso -cyclic anhydrides
Authors: Yang, H. 
Wong, M.W. 
Issue Date: 17-Apr-2013
Citation: Yang, H., Wong, M.W. (2013-04-17). Oxyanion hole stabilization by C-H·O Interaction in a transition state -a three-point interaction model for cinchona alkaloid-catalyzed asymmetric methanolysis of meso -cyclic anhydrides. Journal of the American Chemical Society 135 (15) : 5808-5818. ScholarBank@NUS Repository. https://doi.org/10.1021/ja4005893
Abstract: Oxyanion holes are commonly found in many enzyme structures. They are crucial for the stabilization of high-energy oxyanion intermediates or transition states through hydrogen bonding. Typical functionalities found in enzyme oxyanion holes or chemically designed oxyanion-hole mimics are N-H and O-H groups. Through DFT calculations, we show that asymmetric methanolysis of meso-cyclic anhydrides (AMMA) catalyzed by a class of cinchona alkaloid catalysts involves an oxyanion hole consisting of purely C-H functionality. This C-H oxyanion hole is found to play a pivotal role for stabilizing the developing oxyanion, via C-H·O hydrogen bonds, in our newly proposed three-point interaction transition-state model for AMMA reactions, and is the key reason for the catalyst to adopt the gauche-open conformation in the transition state. Predicted enantioselectivities of three cinchona alkaloid catalysts, namely DHQD-PHN, DHQD-MEQ, and DHQD-CLB, based on calculations of our transition-state model, agree well with experimental findings. © 2013 American Chemical Society.
Source Title: Journal of the American Chemical Society
URI: http://scholarbank.nus.edu.sg/handle/10635/94470
ISSN: 00027863
DOI: 10.1021/ja4005893
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