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Activation of Carboxylic Acids in Asymmetric Organocatalysis
Author(s) -
Monaco Mattia Riccardo,
Poladura Belén,
Diaz de Los Bernardos Miriam,
Leutzsch Markus,
Goddard Richard,
List Benjamin
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201400169
Subject(s) - organocatalysis , enantioselective synthesis , chemistry , catalysis , nucleophile , carboxylic acid , phosphoric acid , supramolecular chemistry , aziridine , combinatorial chemistry , organic chemistry , molecule , ring (chemistry)
Organocatalysis, catalysis using small organic molecules, has recently evolved into a general approach for asymmetric synthesis, complementing both metal catalysis and biocatalysis.1 Its success relies to a large extent upon the introduction of novel and generic activation modes.2 Remarkably though, while carboxylic acids have been used as catalyst directing groups in supramolecular transition‐metal catalysis,3 a general and well‐defined activation mode for this useful and abundant substance class is still lacking. Herein we propose the heterodimeric association of carboxylic acids with chiral phosphoric acid catalysts as a new activation principle for organocatalysis. This self‐assembly increases both the acidity of the phosphoric acid catalyst and the reactivity of the carboxylic acid. To illustrate this principle, we apply our concept in a general and highly enantioselective catalytic aziridine‐opening reaction with carboxylic acids as nucleophiles.