The Mechanism of Class II, Metal-Dependent Aldolases

摘要

The four distinct dihydroxyacctone phosphate dependent aldolases enjoy increasing interest for preparative asymmetric synthesis because of their capacity to build up two new stereo-genie centers with high chiral induction. While all DHAP aldolases have a very broad substrate tolerance for the aldol acceptor substrate, they appear to have a high substrate specificity for dihydroxyaceione phosphate (DHAP) as the al-doi donor, and only few isosteric replacements of the phosphate ester moiety are tolerated. Diastereoselectivity may be limited for certain cases in the control of the stereocenter at C-4. which points to occasional inverse binding of the aldehyde earbonyl group. Certainly, a detailed understanding of the contributions of active site residues in substrate recognition and in the catalytic event is highly desirable to furthcr improve the predictive value of the method.