Phosphoric Acid Based Heterodimers in Asymmetric Catalysis

^‡ These two authors contributed equally.

Abstract

Chiral phosphoric acid diesters arguably constitute the most exploited class of catalysts in asymmetric Brønsted acid catalysis. Despite being highly investigated for their acidic properties, these compounds display an amphoteric nature, which has instead been considerably overlooked. The potential of this dichotomous polarity has recently been disclosed and applied to the development of novel reaction modes in organocatalysis. In this account, we present our recent advances in this area, focusing on the establishment of heterodimeric interactions toward the nucleophilic activation of carboxylic acids, thiocarboxylic acids and ketones (via their enols) in asymmetric transformations.

1 Introduction

2 Discovery of Heterodimeric Self-Assemblies

3 Activation of Carboxylic Acids

3.1 The Enantioselective Carboxylysis of Aziridines

3.2 An Asymmetric Hydrolysis of Epoxides

4 Activation of Thiocarboxylic Acids

5 Enol Catalysis

5.1 Asymmetric Michael Addition

5.2 Asymmetric α-Amination

5.3 Asymmetric α-Allylation

6 Concluding Remarks

Key words

phosphoric acids - non-covalent catalysis - heterodimeric self-assembly - carboxylic acids - enol catalysis - branched ketones

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