In novel bioelectrocatalytic approaches, the functional integration of CO2-fixing enzymes onto electrode materials for the electrosynthesis of stereochemically complex molecules remains to be demonstrated. In this publication, we show the electricity-driven regio- and stereoselective incorporation of CO2 into crotonyl-CoA by an NADPH-dependent enzymatic reductive carboxylation. Co-immobilization of a ferredoxin NADP+ reductase and crotonyl-CoA carboxylase/reductase within a 2,2′-viologen-modified hydrogel enabled iterative NADPH recycling and stereoselective formation of (2S)-ethylmalonyl-CoA, a prospective intermediate towards multi-carbon products from CO2. This approach paves the way for realizing even more complex bioelectrocatalyic cascades in the future.
Leonardo Castañeda-Losada, David Adam, Nicole Paczia, Darren Buesen, Fabian Steffler, Volker Sieber, Tobias J. Erb, Michael Richter, Nicolas Plumeré (2021) Bioelectrocatalytic Cofactor Regeneration Coupled to CO2 Fixation in a Redox-Active Hydrogel for Stereoselective C−C Bond Formation; Angewandte Chemie International Edition 2021, 60, 2–8; https://onlinelibrary.wiley.com/doi/10.1002/anie.202103634