Kinetic Resolution and Desymmetrization of Alcohols and Amines by Nonenzymatic, Enantioselective Acylation

Frost, A. B.; Greenhalgh, M. D.; Munday, E. S.; Musolino, S. F.; Taylor, J. E.; Smith, A.D.


Enantiomerically pure alcohols and amines are ubiquitous throughout Nature and are found within numerous biologically active compounds. This chapter provides a comprehensive overview of strategies for the nonenzymatic acylative kinetic resolution and desymmetrization of alcohols and amines, which have emerged as powerful methods for the preparation of a range of enantiomerically enriched alcohol and amine derivatives. The use of both stoichiometric chiral acylating agents and the use of small-molecule catalysts for such processes is discussed. The chapter provides an overview of the variety of substrates that can be effectively resolved using the range of enantioselective acylation methods available. Key mechanistic considerations within each class of acylation and the origin of stereoselectivity are also discussed.