PUB - Publikationen an der Universität Bielefeld

In this "Concepts"-article, the difficulties in racemizing tertiary alcohols are described as well as a summary of the different chemocatalytic concepts to overcome these hurdles and to pave a way for efficiently racemizing of tertiary alcohols. When combined with the enantioselective enzymatic esterification of tertiary alcohols, the racemization protocols enable a DKR to convert the racemates into enantiomerically pure esters of tertiary alcohols, which are of high interest in the field of pharmaceutically active products. Very recently, various research groups have succeeded in solving the challenging task of identifying suitable chemocatalysts for an efficient racemization of tertiary alcohols and simultaneously suppressing unwanted dehydration side-reactions. It is noteworthy that such methods are based on different, complementary catalysis concepts. Besides Bronsted acids, oxovanadium catalysts as well as piperidine as a representative of an organocatalyst have been found to be useful for the racemization of each type of alcohols. The latter two types of catalysts also turned out to be compatible with lipase-catalyzed kinetic resolution, thus leading to the first two examples of a proof-of-concept for chemoenzymatic DKR of tertiary alcohols. © 2024 Wiley‐VCH GmbH.