Enantioselective Hydrogen Atom Transfer: Discovery of Catalytic Promiscuity in Flavin-Dependent 'Ene'-Reductases

Braddock A. Sandoval; Andrew J. Meichan; Todd K. Hyster

doi:10.1021/jacs.7b05468

Enantioselective Hydrogen Atom Transfer: Discovery of Catalytic Promiscuity in Flavin-Dependent 'Ene'-Reductases

Braddock A. Sandoval
, Andrew J. Meichan
, Todd K. Hyster

Chemistry

Research output: Contribution to journal › Article › peer-review

134 Scopus citations

Abstract

Flavin has long been known to function as a single electron reductant in biological settings, but this reactivity has rarely been observed with flavoproteins used in organic synthesis. Here we describe the discovery of an enantioselective radical dehalogenation pathway for α-bromoesters using flavin-dependent 'ene'-reductases. Mechanistic experiments support the role of flavin hydroquinone as a single electron reductant, flavin semiquinone as the hydrogen atom source, and the enzyme as the source of chirality.

Original language	English (US)
Pages (from-to)	11313-11316
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	139
Issue number	33
DOIs	https://doi.org/10.1021/jacs.7b05468
State	Published - Aug 23 2017

All Science Journal Classification (ASJC) codes

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

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abstract = "Flavin has long been known to function as a single electron reductant in biological settings, but this reactivity has rarely been observed with flavoproteins used in organic synthesis. Here we describe the discovery of an enantioselective radical dehalogenation pathway for α-bromoesters using flavin-dependent 'ene'-reductases. Mechanistic experiments support the role of flavin hydroquinone as a single electron reductant, flavin semiquinone as the hydrogen atom source, and the enzyme as the source of chirality.",

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AU - Meichan, Andrew J.

AU - Hyster, Todd K.

PY - 2017/8/23

Y1 - 2017/8/23

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AB - Flavin has long been known to function as a single electron reductant in biological settings, but this reactivity has rarely been observed with flavoproteins used in organic synthesis. Here we describe the discovery of an enantioselective radical dehalogenation pathway for α-bromoesters using flavin-dependent 'ene'-reductases. Mechanistic experiments support the role of flavin hydroquinone as a single electron reductant, flavin semiquinone as the hydrogen atom source, and the enzyme as the source of chirality.

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UR - https://www.scopus.com/pages/publications/85028082875#tab=citedBy

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IS - 33

ER -

Enantioselective Hydrogen Atom Transfer: Discovery of Catalytic Promiscuity in Flavin-Dependent 'Ene'-Reductases

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