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Catalysis of Hydrogen–Deuterium Exchange Reactions by 4-Substituted Proline Derivatives

Author(s)
Myers, Eddie L.; Palte, Michael J.; Raines, Ronald T
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Abstract
The identification and understanding of structure–activity relationships is vital for rational catalyst design. A kinetic study of the hydrogen–deuterium exchange reaction of cyclohexanone in aqueous solution, as catalyzed by proline derivatives, has revealed valuable structure–activity relationships. In phosphate-buffered solution, cis-4-fluoroproline is more active than the trans isomer, a distinction that appears to originate from a destabilizing interaction between the fluorine atom and phosphate anion during general acid-catalyzed dehydration of the carbinolamine intermediate. trans-4-Ammoniumprolines are exceptionally active catalysts owing to favorable Coulombic interactions involving the ammonium group and the alkoxide moiety formed upon 1,2-addition of the proline derivative to the ketone. These results could be used for the optimization of proline catalysts, especially in transformations where the formation of the putative iminium ion is rate-limiting.
Date issued
2019-01
URI
https://hdl.handle.net/1721.1/123680
Department
Massachusetts Institute of Technology. Department of Chemistry
Journal
Journal of Organic Chemistry
Publisher
American Chemical Society (ACS)
Citation
Myers, Eddie L. et al. "Catalysis of Hydrogen–Deuterium Exchange Reactions by 4-Substituted Proline Derivatives." Journal of Organic Chemistry 84, 3 (January 2019): 1247-1256 © 2019 American Chemical Society
Version: Author's final manuscript
ISSN
0022-3263
1520-6904

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