Direction of Kinetically versus Thermodynamically Controlled Organocatalysis and Its Application in Chemoenzymatic Synthesis

The catalyst loading in the narrow range between 0.5 and 10 mol % determines whether an enantioselective organocatalytic aldol reaction proceeds under kinetic or thermodynamic control; high conversions and ee values can be achieved with low catalyst loadings (see scheme). Since the reaction is carried out in water, it can be combined with a biocatalytic reduction for the one‐pot synthesis of 1,3‐diols with d.r. >25:1 and 99 % ee.