Enantioselective Acylation of Alcohol and Amine Reactions in Organic Synthesis

Enzyme-catalyzed acylation reactions are versatile strategies for the production of esters and amides in optically active form. In this context, hydrolases and mainly lipases have provided efficient access to a myriad of compounds with great selectivity under mild reactions conditions. Although the natural medium for hydrolases is water, the use of this class of enzymes in organic media has been extensively demonstrated, the chemical modification and immobilization of the enzyme being elegant strategies to improve the activity and stability of the catalysts. For that reason, industrial chemical companies have taken advantage of the use of hydrolases for the production of high added value compounds and especially pharmaceuticals by means of the kinetic resolution or desymmetrization strategies. This chapter starts with an introduction dealing with the historical role and advances in the use of hydrolases for synthetic purposes. Then, asymmetric process involving alcohols and amines will be discussed in depth, showing efficient transformations for the production of organic compounds with excellent optical purity and high yields. Examples of classical and dynamic kinetic resolutions of racemates will be shown, giving also attention to the desymmetrization of meso-compounds. In those cases where the use of acylation procedures is not completely efficient, other alternatives such as alkoxycarbonylation reactions will be presented. Overall, the aim of the chapter is to present a simple guideline for the use of hydrolases in organic medium for enantioselective transformations and demonstrate their suitability for the preparation of interesting molecules such as chiral drugs by the selective transformation of adequate intermediates.