Design of 3D‐Printed Heterogeneous Reactor Systems To Overcome Incompatibility Hurdles when Combining Metal and Enzyme Catalysis in a One‐Pot Process

Abstract

AbstractCombining chemo‐ and biocatalysis enables the design of novel economic and sustainable one‐pot processes for the preparation of industrial chemicals, preferably proceeding in water. While a range of proofs‐of‐concept for the compatibility of such catalysts from these two different “worlds of catalysis” have recently been demonstrated, merging noncompatible 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 noncompatible catalyst, substrate or reagent. Exemplified for a one‐pot process consisting of a metal‐catalyzed Wacker oxidation and enzymatic reduction as noncompatible individual reactions steps, we demonstrate that making use of 3D printing of heterogeneous materials containing Cu as a 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.