Core–Shell Composite as the Racemization Catalyst in the Dynamic Kinetic Resolution of Secondary Alcohols

Beta–Silicalite‐1 core–shell microcomposites with controllable shell thickness were synthesized and used as racemization catalysts in the one‐pot dynamic kinetic resolution (DKR) of secondary alcohols by using lipase‐catalyzed transesterification. The inert Silicalite‐1 shell covered the external acidic sites of the Beta zeolite core, suppressing dehydration and non‐enantioselective transesterification of the alcohol. The alcohols could penetrate the Silicalite‐1 shell to access the acidic sites at the core Beta for racemization, however, the enzymatically formed (R)‐esters were excluded owing to their larger size. As a result, the high ee of the (R)‐ester products was conserved and dehydration side products were minimized. Owing to the shape selective nature of the composite racemization catalyst, small and readily available acyl donors could be used in the enzyme‐catalyzed transesterification to obtain the esters with high enantiopurity. The DKR of 1‐phenylethanol with isopropenyl acetate using an optimized core–shell catalyst, CS‐60, gave 92 % selectivity to ester formation and the desired (R)‐1‐phenylethyl acetate was formed with 94 % ee.