Bioinspired molecular transformations by biorelated metal complexes combined with electrolysis and photoredox systems

Naturally-occurring B ₁₂(cobalamin)-dependent enzymes catalyze various molecular transformations that are of particular interest from the viewpoint of biological chemistry as well as synthetic organic chemistry. As bioorganometallic compounds are considered as intermediate for B ₁₂-dependent reactions, those were utilized as catalysts for various molecular transformations. Using the unique property of the B ₁₂ compound, various catalytic reactions have been developed using its model complex. Electroorganic syntheses mediated by the B ₁₂ complex have been developed as green molecular transformations. The redox active B ₁₂ complex shows a unique catalysis in organic synthesis such as the dechlorination of organic halides and the radical mediated isomerization reactions. The B ₁₂ complex-photosensitizer composites have also become a green and efficient catalyst for molecular transformations. The B ₁₂-dependent enzymes mimic reactions catalytically occurring using the B ₁₂ complex-photosensitizer composites. In addition to the B ₁₂ mimic reaction, novel bioinspired reactions were also developed, such as hydrogen production or alkene and alkyne reductions, and the cobalt-hydrogen complex was considered as a putative intermediate of the reactions.