Reaction Mechanisms for Chiral-Phosphate-Catalyzed Transformations Involving Cationic Intermediates and Protic Nucleophiles

Recent strategies for enantioinduction often focus on em-ploying a chiral catalyst to noncovalently interact with the substrate. By restricting the number of low energy diastereomeric transition states the reacting components can adopt, stereoselectivity can be achieved. Many of these noncovalent interactions include a significant dispersive component and these types of contacts have historically been difficult to model accurately. Modern computational methods have been de-signed to overcome such limitations. Using our computational work on chiral phosphate catalysis, we discuss the reasons for enantioselectivity in diverse reaction space. 1 Introduction 2 Chiral Phosphate Catalysis 3 Phosphate-Catalyzed Transfer Hydrogenation 4 Phosphate-Catalyzed Aza-Friedel-Crafts Reaction 5 Phosphate-Catalyzed Reactions Involving Allenamides 6 Comprehensive Qualitative Models 7 Chiral Phosphates and Thionium Intermediates 8 Conclusion

Automated summary

Recent strategies for enantioinduction focus on utilizing a chiral catalyst to noncovalently interact with the substrate. Stereoselectivity can be achieved by limiting the number of low energy diastereomeric transition states that the reacting components can adopt. Modern computational methods have been designed to overcome the difficulties associated with accurately modeling these types of interactions.