Biocatalytic C=C Bond Reduction through Carbon Nanodot‐Sensitized Regeneration of NADH Analogues

• Published in: Angewandte Chemie (International ed.) Vol. 57; no. 42; pp. 13825 - 13828
• Main Authors: Kim, Jinhyun, Lee, Sahng Ha, Tieves, Florian, Choi, Da Som, Hollmann, Frank, Paul, Caroline E., Park, Chan Beum
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 15.10.2018
• Edition: International ed. in English
• Subjects: Adenine; alkene hydrogenation; asymmetric catalysis; Biocatalysis; Carbon; Carbon - chemistry; carbon nanodot; Chemical synthesis; Cofactors; Electrons; Enzymes; NAD; NAD - chemistry; NADH; NADH analogues; Nanostructures - chemistry; Nicotinamide; Nicotinamide adenine dinucleotide; Organic chemistry; photobiocatalysis; Reduction; Regeneration; Stereoselectivity; Substrates; Unsaturated hydrocarbons; alkene hydrogenation; asymmetric catalysis; NADH analogues; photobiocatalysis; carbon nanodot
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201804409

Light‐driven activation of redox enzymes is an emerging route for sustainable chemical synthesis. Among redox enzymes, the family of Old Yellow Enzyme (OYE) dependent on the nicotinamide adenine dinucleotide cofactor (NADH) catalyzes the stereoselective reduction of α,β‐unsaturated hydrocarbons. Here, we report OYE‐catalyzed asymmetric hydrogenation through light‐driven regeneration of NADH and its analogues (mNADHs) by N‐doped carbon nanodots (N‐CDs), a zero‐dimensional photocatalyst. Our spectroscopic and photoelectrochemical analyses verified the transfer of photo‐induced electrons from N‐CDs to an organometallic electron mediator (M) for highly regioselective regeneration of cofactors. Light triggered the reduction of NAD+ and mNAD+s with the cooperation of N‐CDs and M, and the reduction behaviors of cofactors were dependent on their own reduction peak potentials. The regenerated cofactors subsequently delivered hydrides to OYE for stereoselective conversions of a broad range of substrates with excellent biocatalytic efficiencies. Old Yellow Enzyme (OYE) was activated through light‐driven regeneration of nicotinamide adenine dinucleotide cofactor (NADH) and its analogues (mNADHs) by using N‐doped carbon nanodots as a photosensitizer. The photochemically regenerated mNH2H enabled the best catalytic activity of TsOYE. Photochemical regeneration of better‐than‐nature mNADHs can provide an efficient platform for enhancing biocatalytic efficiencies using light energy.