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Selective Activation of C−H Bonds in a Cascade Process Combining Photochemistry and Biocatalysis
Author(s) -
Zhang Wuyuan,
Burek Bastien O.,
FernándezFueyo Elena,
Alcalde Miguel,
Bloh Jonathan Z.,
Hollmann Frank
Publication year - 2017
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.201708668
Subject(s) - biocatalysis , chemistry , ethylbenzene , hydroxylation , hydrogen peroxide , methanol , combinatorial chemistry , photochemistry , stereoselectivity , cascade reaction , organic chemistry , catalysis , enzyme , reaction mechanism
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 2 O 2 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).