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

Joan SerranoPlana | Zendy; Corentin Rumo | Zendy; Johannes G. Rebelein | Zendy; Ryan L. Peterson | Zendy; Maxime Barnet | Zendy; Thomas R. Ward | Zendy

Open Access

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

Author(s) -

Joan SerranoPlana,

Corentin Rumo,

Johannes G. Rebelein,

Ryan L. Peterson,

Maxime Barnet,

Thomas R. Ward

Publication year - 2020

Publication title -

journal of the american chemical society

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 7.115

H-Index - 612

eISSN - 1520-5126

pISSN - 0002-7863

DOI - 10.1021/jacs.0c02788

Subject(s) - chemistry , hydroxylation , streptavidin , biotinylation , cofactor , combinatorial chemistry , kinetic resolution , enantioselective synthesis , ligand (biochemistry) , biocatalysis , catalysis , stereochemistry , biotin , enzyme , organic chemistry , biochemistry , receptor , reaction mechanism

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 H 2 O 2 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.

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