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Stereocontrol in Diphenylprolinol Silyl Ether Catalyzed Michael Additions : Steric Shielding or Curtin-Hammett Scenario?

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Földes, T., Madarász, Á., Révész, Á., Dobi, Z., Varga, S., Hamza, A., Nagy, P. R., Pihko, P., & Pápai, I. (2017). Stereocontrol in Diphenylprolinol Silyl Ether Catalyzed Michael Additions : Steric Shielding or Curtin-Hammett Scenario?. Journal of the American Chemical Society, 139(47), 17052-17063. https://doi.org/10.1021/jacs.7b07097
Published in
Journal of the American Chemical Society
Authors
Földes, Tamás |
Madarász, Ádám |
Révész, Ágnes |
Dobi, Zoltán |
Varga, Szilárd |
Hamza, Andrea |
Nagy, Péter R. |
Pihko, Petri |
Pápai, Imre
Date
2017
Discipline
Orgaaninen kemiaNanoscience CenterOrganic ChemistryNanoscience Center
Copyright
© 2017 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.

 
The enantioselectivity of amine-catalyzed reactions of aldehydes with electrophiles is often explained by simple steric arguments emphasizing the role of the bulky group of the catalyst that prevents the approach of the electrophile from the more hindered side. This standard steric shielding model has recently been challenged by the discovery of stable downstream intermediates, which appear to be involved in the rate-determining step of the catalytic cycle. The alternative model, referred to as Curtin-Hammett scenario of stereocontrol, assumes that the enantioselectivity is related to the stability and reactivity of downstream intermediates. In our present computational study, we examine the two key processes of the catalytic Michael reaction between propanal and β-nitrostyrene that are relevant to the proposed stereoselectivity models, namely the C-C bond formation and the protonation steps. The free energy profiles obtained for the pathways leading to the enantiomeric products suggest that the rate- and stereo-determining steps are not identical as implied by the previous models. The stereoselectivity can be primarily controlled by C-C bond formation even though the reaction rate is dictated by the protonation step. This kinetic scheme is consistent with all observations of experimental mechanistic studies including those of mass spectrometric back reaction screening experiments, which reveal a mismatch between the stereoselectivity of the back and the forward reactions. ...
Publisher
American Chemical Society
ISSN Search the Publication Forum
0002-7863
Keywords
organocatalysis mechanism stereocontrol DFT kinetics ESI-MS screening
DOI
https://doi.org/10.1021/jacs.7b07097
URI

http://urn.fi/URN:NBN:fi:jyu-201711304428

Publication in research information system

https://converis.jyu.fi/converis/portal/detail/Publication/27320825

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