Abstract
Recent strategies for enantioinduction often focus on employing 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 designed 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
Key words
organocatalysis - enantioselectivity - chiral phosphoric acids - density functional
theory - noncovalent interactions
