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http://hdl.handle.net/2445/142779
Title: | Bifunctional tripeptide with a phosphonic acid as a bronsted acid for Michael addition: mechanistic insights |
Author: | Cortes-Clerget, Margery Jover Modrego, Jesús Dussart, Jade Kolodziej, Emilie Monteil, Maelle Migianu-Griffoni, Evelyne Gager, Olivier Deschamp, Julia Lecouvey, Marc |
Keywords: | Reaccions d'addició Teoria del funcional de densitat Catàlisi Addition reactions Density functionals Catalysis |
Issue Date: | 11-May-2017 |
Publisher: | Wiley-VCH |
Abstract: | Enamine catalysis is a widespread activation mode in the field of organocatalysis and is often encountered in bifunctional organocatalysts. We previously described H-Pro-Pro-pAla-OMe as a bifunctional catalyst for Michael addition between aldehydes and aromatic nitroalkenes. Considering that opposite selectivities were observed when compared to H-Pro-Pro-Glu-NH2, an analogue described by Wennemers, the activation mode of H-Pro-Pro-pAla-OMe was investigated through kinetic, linear effect studies, NMR analyses, and structural modifications. It appeared that only one bifunctional catalyst was involved in the catalytic cycle, by activating aldehyde through an (E)-enamine and nitroalkene through an acidic interaction. A restrained tripeptide structure was optimal in terms of distance and rigidity for better selectivities and fast reaction rates. Transition-state modeling unveiled the particular selectivity of this phosphonopeptide. |
Note: | Versió postprint del document publicat a: https://doi.org/10.1002/chem.201700604 |
It is part of: | Chemistry-A European Journal, 2017, vol. 23, num. 27, p. 6654-6662 |
URI: | http://hdl.handle.net/2445/142779 |
Related resource: | https://doi.org/10.1002/chem.201700604 |
ISSN: | 0947-6539 |
Appears in Collections: | Articles publicats en revistes (Química Inorgànica i Orgànica) |
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