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Evidence for the Importance of Polarizability in Biomimetic Catalysis Involving Cyclophane Receptors

Ngola, Sarah M. and Dougherty, Dennis A. (1996) Evidence for the Importance of Polarizability in Biomimetic Catalysis Involving Cyclophane Receptors. Journal of Organic Chemistry, 61 (13). pp. 4355-4360. ISSN 0022-3263. doi:10.1021/jo960521y.

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Cyclophanes 1−6 catalyze the nucleophilic dealkylation of a simple sulfonium compound by potassium iodide. The cation−π interaction is important in substrate binding, but the primarily electrostatic nature of this effect does not explain all observations concerning catalysis. As a series of substituents are placed on the cyclophane framework, a systematic variation in catalyst effectiveness is seen, such that more polarizable substituents produce more potent catalysts. This provides support for the notion that transition states are especially polarizable, and catalysis can be enhanced by maximizing London dispersion forces. The reactions studied here are very similar to the broad class of biological methylations mediated by S-adenosylmethionine, and the biological catalysts may use forces similar to those described here.

Item Type:Article
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Dougherty, Dennis A.0000-0003-1464-2461
Additional Information:© 1996 American Chemical Society. Received March 18, 1996. We thank the Office of Naval Research for support of this work. We also thank Dr. Alison McCurdy for assistance with initial experiments and many helpful discussions, and Dr. Jonathan Forman for assistance with the CD measurements and calculations. Recipient of a General Electric fellowship and an NSF predoctoral fellowship.
Funding AgencyGrant Number
Office of Naval Research (ONR)UNSPECIFIED
General ElectricUNSPECIFIED
NSF Predoctoral FellowshipUNSPECIFIED
Subject Keywords:Polarizability, Transition states, Substituents, Aromatic compounds, Catalysis
Issue or Number:13
Record Number:CaltechAUTHORS:20200612-115646505
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Official Citation:Sarah M. Ngola and Dennis A. Dougherty The Journal of Organic Chemistry 1996 61 (13), 4355-4360 DOI: 10.1021/jo960521y
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:103875
Deposited By: George Porter
Deposited On:12 Jun 2020 20:33
Last Modified:16 Nov 2021 18:26

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