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Asymmetric aza-Henry reaction under phase transfer catalysis: An experimental and theoretical study - Zurich Open Repository and Archive


Gomez-Bengoa, E; Linden, A; Lopez, R; Mugica-Mendiola, I; Oiarbide, M; Palomo, C (2008). Asymmetric aza-Henry reaction under phase transfer catalysis: An experimental and theoretical study. Journal of the American Chemical Society, 130(25):7955-7966.

Abstract

An efficient catalytic asymmetric aza-Henry reaction under phase transfer conditions is presented.
The method is based on the reaction of the respective nitroalkane with R-amido sulfones effected by
CsOH·H2O base in toluene as solvent and in the presence of cinchone-derived ammonium catalysts. This
direct aza-Henry reaction presents as interesting features its validity for both nonenolizable and enolizable
aldehyde-derived azomethines and the tolerance of nitroalkanes, other than nitromethane, for the production
of -nitroamines. The synthetic value of the methodology described is demonstrated by providing (a) a
direct route for the asymmetric synthesis of differently substituted 1,2-diamines and (b) a new asymmetric
synthesis of γ-amino R, -unsaturated esters through a catalytic, highly enantioselective formal addition of
functionalized alkenyl groups to azomethines. Finally, a preferred TS that nicely fits the observed
enantioselectivity has been identified. Most remarkable, an unusual hydrogen bond pattern for the catalystnitrocompound-
imine complex is predicted, where the catalyst OH group interacts with the NO2 group of
the nitrocompound.

Abstract

An efficient catalytic asymmetric aza-Henry reaction under phase transfer conditions is presented.
The method is based on the reaction of the respective nitroalkane with R-amido sulfones effected by
CsOH·H2O base in toluene as solvent and in the presence of cinchone-derived ammonium catalysts. This
direct aza-Henry reaction presents as interesting features its validity for both nonenolizable and enolizable
aldehyde-derived azomethines and the tolerance of nitroalkanes, other than nitromethane, for the production
of -nitroamines. The synthetic value of the methodology described is demonstrated by providing (a) a
direct route for the asymmetric synthesis of differently substituted 1,2-diamines and (b) a new asymmetric
synthesis of γ-amino R, -unsaturated esters through a catalytic, highly enantioselective formal addition of
functionalized alkenyl groups to azomethines. Finally, a preferred TS that nicely fits the observed
enantioselectivity has been identified. Most remarkable, an unusual hydrogen bond pattern for the catalystnitrocompound-
imine complex is predicted, where the catalyst OH group interacts with the NO2 group of
the nitrocompound.

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102 citations in Web of Science®
108 citations in Scopus®
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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:30 May 2008
Deposited On:07 Jan 2009 13:24
Last Modified:05 Apr 2016 12:44
Publisher:American Chemical Society
ISSN:0002-7863
Funders:University of the Basque Country (UPV/EHU), Ministerio de Educación y Ciencia (MEC)
Publisher DOI:https://doi.org/10.1021/ja800253z

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