Photobiocatalytic Enantioselective Benzylic C(sp3)–H Acylation Enabled by Thiamine-Dependent Enzymes via Intermolecular Hydrogen Atom Transfer DOI
Yen‐Chu Lu,

Ronald D. Adukure,

Satyajit Roy

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 14, 2025

Hydrogen atom transfer (HAT) constitutes a powerful mechanism exploited in biology and chemistry to functionalize ubiquitous C(sp3)-H bonds organic molecules. Despite its synthetic potential, achieving stereocontrol chemical HAT-mediated C-H functionalization transformations remains challenging. By merging the radical reactivity of thiamine (ThDP)-dependent enzymes with hydrogen transfer, we report here photobiocatalytic strategy for enantioselective acylation an substrate, transformation not found nature nor currently attainable by means. This method enables direct benzylic sites broad range substrates furnish valuable enantioenriched ketone motifs good high enantioselectivity (up 96% ee). Mechanistic spectroscopic studies support involvement species derived from Breslow intermediate highlight critical role photocatalyst abstraction reagents productive catalysis, reveal specific enzyme/photocatalyst interaction favoring single electron during catalysis. Further insights into how C-C bond-forming reaction is controlled enzyme influenced active site mutations were gained via molecular modeling. study illustrates integration ThDP-mediated biocatalysis HAT, expanding asymmetric that can be accessed through biocatalysis.

Language: Английский

Aryne Alder-Ene Reaction Enables Arylation of Conformationally Locked Styrenes DOI
Tamal Ballav, S. C. Barman, Venkataraman Ganesh

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 15, 2025

We report a transition metal-free aryne Alder-ene (AAE) reaction of conformationally locked styrenes like methylene indane (5,6-fusion) and tetralin (6,6-fusion) to provide aryl-decorated indenes dihydronaphthalenes. DFT studies compared the states between 5,6- 6,6-fused systems. The synthetic utility products was demonstrated.

Language: Английский

Citations

0
Photobiocatalytic Enantioselective Benzylic C(sp3)–H Acylation Enabled by Thiamine-Dependent Enzymes via Intermolecular Hydrogen Atom Transfer DOI
Yen‐Chu Lu,

Ronald D. Adukure,

Satyajit Roy

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 14, 2025

Hydrogen atom transfer (HAT) constitutes a powerful mechanism exploited in biology and chemistry to functionalize ubiquitous C(sp3)-H bonds organic molecules. Despite its synthetic potential, achieving stereocontrol chemical HAT-mediated C-H functionalization transformations remains challenging. By merging the radical reactivity of thiamine (ThDP)-dependent enzymes with hydrogen transfer, we report here photobiocatalytic strategy for enantioselective acylation an substrate, transformation not found nature nor currently attainable by means. This method enables direct benzylic sites broad range substrates furnish valuable enantioenriched ketone motifs good high enantioselectivity (up 96% ee). Mechanistic spectroscopic studies support involvement species derived from Breslow intermediate highlight critical role photocatalyst abstraction reagents productive catalysis, reveal specific enzyme/photocatalyst interaction favoring single electron during catalysis. Further insights into how C-C bond-forming reaction is controlled enzyme influenced active site mutations were gained via molecular modeling. study illustrates integration ThDP-mediated biocatalysis HAT, expanding asymmetric that can be accessed through biocatalysis.

Language: Английский

Citations

0