Solar-driven biocatalytic C-hydroxylation through direct transfer of photoinduced electrons

• Published in: Green chemistry : an international journal and green chemistry resource : GC Vol. 21; no. 3; pp. 515 - 525
• Main Authors: Le, Thien-Kim, Park, Jong Hyun, Choi, Da Som, Lee, Ga-Young, Choi, Woo Sung, Jeong, Ki Jun, Park, Chan Beum, Yun, Chul-Ho
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 04.02.2019
• Subjects: Chemical industry; Dependence; Electrons; Flavin mononucleotide; Green chemistry; Heme; Hydroxylation; Iron; Lauric acid; NADP; NADPH; Nicotinamide; Nitrophenol; Organic chemistry; Photoactivation; Reductase
• ISSN: 1463-9262; 1463-9270
• DOI: 10.1039/c8gc02398k

Despite the immense potential of P450s, the dependence on the nicotinamide cofactor (NADPH) and NADPH-P450 reductase (CPR) limits their employment in the chemical industry. Here, we present a visible light-driven platform for biocatalytic C-hydroxylation reactions using natural flavin molecules, especially flavin mononucleotide, as a photosensitizer. By employing visible light as a source of energy instead of the nicotinamide cofactor, the bacterial CYP102A1 heme domain was successfully applied for photobiocatalytic C-hydroxylation of 4-nitrophenol and lauric acid - in the absence of NADPH and CPR. We present a proof of concept that the photoactivation of flavins is productively coupled with the direct transfer of photoinduced electrons to the P450 heme iron, achieving photobiocatalytic C-hydroxylation reactions. Photoactivation of flavins is coupled productively with the direct transfer of photoinduced electrons to P450s to achieve photobiocatalytic C-hydroxylation reactions in the absence of nicotinamide cofactors.