TY - JOUR
T1 - Enantioselective Hydrogen Atom Transfer
T2 - Discovery of Catalytic Promiscuity in Flavin-Dependent 'Ene'-Reductases
AU - Sandoval, Braddock A.
AU - Meichan, Andrew J.
AU - Hyster, Todd K.
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/8/23
Y1 - 2017/8/23
N2 - 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.
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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U2 - 10.1021/jacs.7b05468
DO - 10.1021/jacs.7b05468
M3 - Article
C2 - 28780870
AN - SCOPUS:85028082875
SN - 0002-7863
VL - 139
SP - 11313
EP - 11316
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 33
ER -