Selective Activation of C−H Bonds in a Cascade Process Combining Photochemistry and Biocatalysis. Issue 48 (3rd November 2017)

• Record Type: Journal Article
• Authors: Zhang, Wuyuan; Burek, Bastien O.; Fernández‐Fueyo, Elena; Alcalde, Miguel; Bloh, Jonathan Z.; Hollmann, Frank
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 48(2017)
• Page Start: 15451
• Page End: 15455
• Publication Date: 2017-11-03
• Subjects: Biocatalysis -- oxyfunctionalization -- peroxygenases -- photocatalysis -- TiO2; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201708668
• Languages: English
• ISSNs: 1433-7851

Abstract

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). Abstract : Inorganic photocatalysis with Au‐TiO2 and selective enzymatic catalysis were combined for the oxyfunctionalization of inert C−H bonds. The hydroxylation of ethylbenzene to ( R )‐1‐phenylethanol was thus achieved with high enantioselectivity and excellent turnover numbers.