Enantioselective Hydroxylation of Benzylic C(sp(3))-H Bonds by an Artificial 
Iron Hydroxylase Based on the Biotin-Streptavidin Technology

Serrano-Plana, J.; Rumo, C.; Rebelein, J. G.; Peterson, R. L.; Barnet, M.; Ward, T. R.

doi:10.1021/jacs.0c02788

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Enantioselective Hydroxylation of Benzylic C(sp(3))-H Bonds by an Artificial Iron Hydroxylase Based on the Biotin-Streptavidin Technology

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https://www.ncbi.nlm.nih.gov/pubmed/32450689
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Serrano-Plana, J., Rumo, C., Rebelein, J. G., Peterson, R. L., Barnet, M., & Ward, T. R. (2020). Enantioselective Hydroxylation of Benzylic C(sp(3))-H Bonds by an Artificial Iron Hydroxylase Based on the Biotin-Streptavidin Technology. J Am Chem Soc, 142(24), 10617-10623. doi:10.1021/jacs.0c02788.

Cite as: https://hdl.handle.net/21.11116/0000-0008-F1D8-4

Abstract

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 approximately 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.