Apr 2013 - Review on Asymmetric Acylation Published

Organocatalytic asymmetric acylation is a fast-moving area of current research. This chapter overviews latest developments and future prospects.

Alan C. Spivey and Stellios Arseniyadis ‘Kinetic Resolution and Asymmetric Desymmetrization by Enantioselective Acylation and Related Processes’ in Comprehensive Enantioselective Organocatalysis, Ed. Peter Dalko, Wiley-VCH, 2013, Volume 3, Chapter 41, 1225-1284 (ISBN 978-3-527-33236-6).

The use of enantiomerically enriched small molecule chiral nucleophiles as orga­nocatalysts for the asymmetric preparation of various important classes of chiral fine chemicals has been intensively investigated over the last two decades. Initial focus centered largely on the acylative kinetic resolution (KR) and asymmetric desymmetrization (ASD) of racemic secondary alcohols and meso-diols, respectively, to give the corresponding esters using substoichiometric amounts of various nucleophilic chiral amines and phosphines in conjunction with stoichiometric quantities of appropriate acyl donors. Increasingly, however, and reflecting the rapid maturation of this field, attention is broadening to encompass mechanistically related processes for the asymmetric phosphorylation, phosphitylation, sulfonylation, sulfinylation, and silylation of alcohols and for the asymmetric acylation of amines and of carbon nucleophiles. Since the historical development of the field as well as many of the more recent advances have been comprehensively reviewed, this review is designed to provide an update on recent developments with a particular emphasis on current challenges and trends in nucleophile-catalyzed asymmetric group transfer to oxygen and nitrogen atoms; related transformations involving acyl and carboxyl transfer to carbon (e.g., [1,3]-Steglich-type rearrangements) have not been included.