Nonlinear effects in asymmetric catalysis mediated by amino alcohol ligands

ORGN 114

Tom Wyczesany, t.wyczesany@chem.usyd.edu.au and Matthew H. Todd. School of Chemistry, University of Sydney, Eastern Avenue, NSW 2006, Sydney, Australia
The catalytic generation of enantiomerically pure compounds remains one of the most powerful and challenging aspects of organic chemistry. It is reasonable to expect a linear relationship between the enantiomeric excess (e.e.) of the product of a catalytic asymmetric reaction, and the catalyst or ligand employed in that reaction. In fact there are many cases known where there is a nonlinear relation between these parameters. These Nonlinear Effects (NLEs) operate in several distinct ways, but perhaps most strikingly can generate very high product e.e. in reactions where a catalyst is nearly racemic. A well-known example is the addition of diethylzinc to benzaldehyde catalysed by Noyori's DAIB. (The dramatic influence such effects can have on organic reactions is at odds with how little is known of their scope). In this work several sets of ligands has been examined such as amino alcohols and amino thiols which are derivatives of amino acids. Experimental work has been compared with computational methods to try to develop a predictive model.