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Bioelectrocatalytic Cofactor Regeneration Coupled to CO 2 Fixation in a Redox‐Active Hydrogel for Stereoselective C−C Bond Formation
Author(s) -
CastañedaLosada Leonardo,
Adam David,
Paczia Nicole,
Buesen Darren,
Steffler Fabian,
Sieber Volker,
Erb Tobias J.,
Richter Michael,
Plumeré Nicolas
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202103634
Subject(s) - stereoselectivity , carbon fixation , carboxylation , chemistry , faraday efficiency , cofactor , artificial photosynthesis , pyruvate carboxylase , combinatorial chemistry , reductase , redox , stereochemistry , photochemistry , electrochemistry , enzyme , catalysis , photosynthesis , biochemistry , electrode , organic chemistry , photocatalysis
The sustainable capture and conversion of carbon dioxide (CO 2 ) is key to achieving a circular carbon economy. Bioelectrocatalysis, which aims at using renewable energies to power the highly specific, direct transformation of CO 2 into value added products, holds promise to achieve this goal. However, the functional integration of CO 2 ‐fixing enzymes onto electrode materials for the electrosynthesis of stereochemically complex molecules remains to be demonstrated. Here, we show the electricity‐driven regio‐ and stereoselective incorporation of CO 2 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 CO 2 , with 92±6 % faradaic efficiency and at a rate of 1.6±0.4 μmol cm −2 h −1 . This approach paves the way for realizing even more complex bioelectrocatalyic cascades in the future.