Please use this identifier to cite or link to this item: https://doi.org/10.1021/ja4005893
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dc.titleOxyanion 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
dc.contributor.authorYang, H.
dc.contributor.authorWong, M.W.
dc.date.accessioned2014-10-16T08:36:24Z
dc.date.available2014-10-16T08:36:24Z
dc.date.issued2013-04-17
dc.identifier.citationYang, 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
dc.identifier.issn00027863
dc.identifier.urihttp://scholarbank.nus.edu.sg/handle/10635/94470
dc.description.abstractOxyanion 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.
dc.description.urihttp://libproxy1.nus.edu.sg/login?url=http://dx.doi.org/10.1021/ja4005893
dc.sourceScopus
dc.typeArticle
dc.contributor.departmentCHEMISTRY
dc.description.doi10.1021/ja4005893
dc.description.sourcetitleJournal of the American Chemical Society
dc.description.volume135
dc.description.issue15
dc.description.page5808-5818
dc.description.codenJACSA
dc.identifier.isiut000317872800046
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