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Selective Activation of C-H Bonds in a Cascade Process Combining Photochemistry and Biocatalysis.

ABSTRACT: Selective oxyfunctionalizations of inert C-H bonds can be achieved under mild conditions by using peroxygenases. This approach, however, suffers from the poor robustness of these enzymes in the presence of hydrogen peroxide as the stoichiometric oxidant. Herein, we demonstrate that inorganic photocatalysts such as gold-titanium dioxide efficiently provide H₂ O₂ through the methanol-driven reductive activation of ambient oxygen in amounts that ensure that the enzyme remains highly active and stable. Using this approach, the stereoselective hydroxylation of ethylbenzene to (R)-1-phenylethanol was achieved with high enantioselectivity (>98?% ee) and excellent turnover numbers for the biocatalyst (>71?000).

SUBMITTER: Zhang W

PROVIDER: S-EPMC5725739 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature

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Selective Activation of C-H Bonds in a Cascade Process Combining Photochemistry and Biocatalysis.

Zhang Wuyuan W Burek Bastien O BO Fernández-Fueyo Elena E Alcalde Miguel M Bloh Jonathan Z JZ Hollmann Frank F

Angewandte Chemie (International ed. in English) 20171103 48

Selective oxyfunctionalizations of inert C-H bonds can be achieved under mild conditions by using peroxygenases. This approach, however, suffers from the poor robustness of these enzymes in the presence of hydrogen peroxide as the stoichiometric oxidant. Herein, we demonstrate that inorganic photocatalysts such as gold-titanium dioxide efficiently provide H<sub>2</sub> O<sub>2</sub> through the methanol-driven reductive activation of ambient oxygen in amounts that ensure that the enzyme remains ...[more]

PMID: 28994504

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