Enantioselective Hydroxylation of Benzylic C(sp3)-H Bonds by an Artificial Iron Hydroxylase Based on the Biotin-Streptavidin Technology

Article abstract of DOI:10.1021/jacs.0c02788

The selective hydroxylation of C-H bonds is of great interest to the synthetic community. Both homogeneous catalysts and enzymes offer complementary means to tackle this challenge. Herein, we show that biotinylated Fe(TAML)-complexes (TAML = Tetra Amido Macrocyclic Ligand) can be used as cofactors for incorporation into streptavidin to assemble artificial hydroxylases. Chemo-genetic optimization of both cofactor and streptavidin allowed optimizing the performance of the hydroxylase. Using H₂O₂ as oxidant, up to ～300 turnovers for the oxidation of benzylic C-H bonds were obtained. Upgrading the ee was achieved by kinetic resolution of the resulting benzylic alcohol to afford up to >98% ee for (R)-tetralol. X-ray analysis of artificial hydroxylases highlights critical details of the second coordination sphere around the Fe(TAML) cofactor.

Full text of DOI:10.1021/jacs.0c02788

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Communication
Enantioselective Hydroxylation of Benzylic C(sp3)-H Bonds by an Artificial Iron Hydroxylase Based on the Biotin-Streptavidin Technology
Joan Serrano-Plana, Corentin Rumo, Johannes G. Rebelein, Ryan Loren Peterson, Maxime Barnet, and Thomas R. Ward
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c02788 • Publication Date (Web): 26 May 2020
Downloaded from pubs.acs.org on May 26, 2020
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ACS Paragon Plus Environment

Page 13 of 14
Journal of the American Chemical Society
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 14 of 14
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ACS Paragon Plus Environment