Bio-inspired Chiral Primary Amine Catalysis

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