Organocatalysis: acylation catalysts

This review shows how experimental and theoretical methods can help chemists to clarify the mechanism of acylation reactions and subsequently use this insight to develop improved acylation catalysts. Theoretical methods can be used in this context in a variety of ways, starting from the structural optimization of reactants, products, and reaction intermediates up to the full characterization of potential energy surfaces. Whether, in the end, all of this is necessary for the theory-guided development of acylation catalysts is discussed in the last section of this review. The most challenging area in acylation catalyst development remains that of stereoselective catalysis, in which major advances have recently been made, but where theoretical prediction of catalyst selectivity is still exceedingly rare. (C) 2011 John Wiley & Sons, Ltd. WIREs Comput Mol Sci 2011 1 601-619 DOI:10.1002/wcms.48