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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
Addition reactions
Density functionals
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:
It is part of: Chemistry-A European Journal, 2017, vol. 23, num. 27, p. 6654-6662
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ISSN: 0947-6539
Appears in Collections:Articles publicats en revistes (Química Inorgànica i Orgànica)

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