@article{6735264f453c45ce973cb279dae57253,
title = "Quaternary Charge-Transfer Complex Enables Photoenzymatic Intermolecular Hydroalkylation of Olefins",
abstract = "Intermolecular C-C bond-forming reactions are underdeveloped transformations in the field of biocatalysis. Here we report a photoenzymatic intermolecular hydroalkylation of olefins catalyzed by flavin-dependent 'ene'-reductases. Radical initiation occurs via photoexcitation of a rare high-order enzyme-templated charge-transfer complex that forms between an alkene, α-chloroamide, and flavin hydroquinone. This unique mechanism ensures that radical formation only occurs when both substrates are present within the protein active site. This active site can control the radical terminating hydrogen atom transfer, enabling the synthesis of enantioenriched γ-stereogenic amides. This work highlights the potential for photoenzymatic catalysis to enable new biocatalytic transformations via previously unknown electron transfer mechanisms.",
author = "Page, {Claire G.} and Cooper, {Simon J.} and Dehovitz, {Jacob S.} and Oblinsky, {Daniel G.} and Biegasiewicz, {Kyle F.} and Antropow, {Alyssa H.} and Armbrust, {Kurt W.} and Ellis, {J. Michael} and Hamann, {Lawrence G.} and Horn, {Evan J.} and Oberg, {Kevin M.} and Scholes, {Gregory D.} and Hyster, {Todd K.}",
note = "Funding Information: Reaction optimization and substrate scope explorations were supported by the National Institutes of Health (NIH) National Institute of General Medical Sciences (NIGMS) (R01 GM127703) and Bristol-Myers-Squibb as part of the Princeton Catalysis Initiative (T.K.H.). Mechanistic experiments, including and transient absorption and UV–vis spectroscopy, were supported by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy (DOE) through grant DE-SC0019370. We acknowledge the MacMillan Group for the use of their instrumentation. D.G.O. acknowledges support from the Postgraduate Scholarships Doctoral Program of the Natural Sciences and Engineering Research Council of Canada. C.G.P. acknowledges the NSF-GRFP for support. J.S.D. acknowledges support from the Bristol-Myers-Squibb Graduate Fellowship. Publisher Copyright: {\textcopyright} ",
year = "2021",
month = jan,
day = "13",
doi = "10.1021/jacs.0c11462",
language = "English (US)",
volume = "143",
pages = "97--102",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "1",
}