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Remote stereocontrol with azaarenes via enzymatic hydrogen atom transfer
Abstract
Strategies for achieving asymmetric catalysis with azaarenes have traditionally fallen short of accomplishing remote stereocontrol, which would greatly enhance accessibility to distinct azaarenes with remote chiral centres. The primary obstacle to achieving superior enantioselectivity for remote stereocontrol has been the inherent rigidity of the azaarene ring structure. Here we introduce an ene-reductase system capable of modulating the enantioselectivity of remote carbon-centred radicals on azaarenes through a mechanism of chiral hydrogen atom transfer. This photoenzymatic process effectively directs prochiral radical centres located more than six chemical bonds, or over 6 Å, from the nitrogen atom in azaarenes, thereby enabling the production of a broad array of azaarenes possessing a remote γ-stereocentre. Finally, results from our integrated computational and experimental investigations underscore that the hydrogen bonding and steric effects of key amino acid residues are important for achieving such high stereoselectivities.
- Publication Date:
- Research Org.:
- Center for Advanced Bioenergy and Bioproducts Innovation (CABBI), Urbana, IL (United States); Univ. of Illinois at Urbana-Champaign, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 2309735
- Grant/Contract Number:
- SC0018420
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Chemistry
- Additional Journal Information:
- Journal Volume: 16; Journal Issue: 2; Journal ID: ISSN 1755-4330
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; asymmetric catalysis; biocatalysis; photocatalysis
Citation Formats
Li, Maolin, Harrison, Wesley, Zhang, Zhengyi, Yuan, Yujie, and Zhao, Huimin. Remote stereocontrol with azaarenes via enzymatic hydrogen atom transfer. United States: N. p., 2023.
Web. doi:10.1038/s41557-023-01368-x.
Li, Maolin, Harrison, Wesley, Zhang, Zhengyi, Yuan, Yujie, & Zhao, Huimin. Remote stereocontrol with azaarenes via enzymatic hydrogen atom transfer. United States. https://doi.org/10.1038/s41557-023-01368-x
Li, Maolin, Harrison, Wesley, Zhang, Zhengyi, Yuan, Yujie, and Zhao, Huimin. Thu .
"Remote stereocontrol with azaarenes via enzymatic hydrogen atom transfer". United States. https://doi.org/10.1038/s41557-023-01368-x.
@article{osti_2309735,
title = {Remote stereocontrol with azaarenes via enzymatic hydrogen atom transfer},
author = {Li, Maolin and Harrison, Wesley and Zhang, Zhengyi and Yuan, Yujie and Zhao, Huimin},
abstractNote = {Strategies for achieving asymmetric catalysis with azaarenes have traditionally fallen short of accomplishing remote stereocontrol, which would greatly enhance accessibility to distinct azaarenes with remote chiral centres. The primary obstacle to achieving superior enantioselectivity for remote stereocontrol has been the inherent rigidity of the azaarene ring structure. Here we introduce an ene-reductase system capable of modulating the enantioselectivity of remote carbon-centred radicals on azaarenes through a mechanism of chiral hydrogen atom transfer. This photoenzymatic process effectively directs prochiral radical centres located more than six chemical bonds, or over 6 Å, from the nitrogen atom in azaarenes, thereby enabling the production of a broad array of azaarenes possessing a remote γ-stereocentre. Finally, results from our integrated computational and experimental investigations underscore that the hydrogen bonding and steric effects of key amino acid residues are important for achieving such high stereoselectivities.},
doi = {10.1038/s41557-023-01368-x},
journal = {Nature Chemistry},
number = 2,
volume = 16,
place = {United States},
year = {Thu Nov 16 00:00:00 EST 2023},
month = {Thu Nov 16 00:00:00 EST 2023}
}
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