PUB - Publikationen an der Universität Bielefeld

Combining chemo- and biocatalysis enables the design of novel economic and sustainable one-pot processes to industrial chemicals, preferably proceeding in water. While a range of proof-of-concepts for the compatibility of such catalysts from these two different "worlds of catalysis" have recently been demonstrated, merging non-compatible chemo- and biocatalysts for joint applications within one reactor remained a challenge. A conceptual solution is compartmentalization of the catalytic moieties by heterogenization of critical catalyst components, thus "shielding" them from the complementary non-compatible catalyst, substrate or reagent. Exemplified for a one-pot process consisting of a metal-catalyzed Wacker oxidation and enzymatic reduction as non-compatible individual reactions steps, we demonstrate that making use of 3D-printing of heterogeneous materials containing Cu as critical metal component can overcome such incompatibility hurdles. The application of a 3D-printed Cu-ceramic device as metal catalyst component allows an efficient combination with the enzyme and the desired two-step transformation of styrene into the chiral alcohol product with high overall conversion and excellent enantioselectivity. This compartmentalization concept based on 3D-printing of heterogenized metal catalysts represents a scalable methodology and opens up numerous perspectives to be used as a general tool also for other related chemoenzymatic research challenges. © 2024 Wiley-VCH GmbH.