Bio-inspired Chiral Primary Amine Catalysis

Abstract

The search for new catalysts with superior performance and broad applicability remains a central theme in asymmetric organocatalysis. Inspired by Nature as well as by numerous previous efforts, we have developed chiral primary–tertiary diamines as both functional and mechanistic enzyme mimics, showing unprecedented scope in enamine-aldol reactions and significant potential in the reactions of acroleins. Our endeavors focusing on this type of catalysts are summarized in this account.

1 Introduction

2 General Features of Primary–Tertiary Vicinal Diamine/TfOH; Multifunctional Catalysis

3 Asymmetric Supramolecular Primary Amine Catalysis; Roles of the Hydrophobic Cavity

4 Asymmetric Direct Aldol Reaction of Aliphatic Ketones

5 Asymmetric Direct Cross-Aldol Reaction of Aldehydes

6 Asymmetric Retro-Aldol and Transfer-Aldol Reactions

7 Iminium Catalysis with Chiral Primary–Tertiary Diamines

8 Bifunctional Catalysis of Primary–Tertiary Diamines in the Baylis–Hillman Reaction

9 Conclusion, Remarks, and Outlook

Key words

primary amines - organocatalysts - aldol reaction - enamines - iminium

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