N‐Oxyl Radicals in Oxidative C–O Coupling: Free‐Radical Hydrogen Substitution and Addition to C=C Bonds DOI
Elena R. Lopat’eva, Igor B. Krylov, Bing Yu

et al.

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 18, 2024

Abstract N ‐oxyl radicals occupy an important place in free‐radical oxidative CH‐functionalization being one of the most efficient redox‐organocatalysts for hydrogen atom abstraction (HAT). Their applications include aerobic radical chain autoxidation, with formation carbon‐carbon and carbon‐heteroatom bonds. The persistent nature N‐ oxyl combined their high reactivity HAT results unique dual chemistry: same can both propagate reaction (at low concentrations) effectively “terminate” carbon‐centered higher concentrations). latter case opens a new synthetic application area radicals, which they act as abstracting species O‐reagents cross‐coupling thus produced. Apart from C−H bond cleavage, reactive have been extensively used recently C=C double functionalization via addition reactions. In this review, reactions introduction fragments alkene difunctionalizations by oxyls are covered emphasis on relationship between conditions selectivity.

Language: Английский

Catalytic photoinduced deoxygenation via B(C6F5)3-enabled OAT for aromatic C−H amination of alkylarenes DOI
Yongmin Ma

Research Square (Research Square), Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

Abstract The catalytic deoxygenation of N − OH bonds to generate N-centered radicals remains a significant challenge due the high bond dissociation energy and reliance on stoichiometric auxiliaries or activators. Herein, we report B(C6F5)3-catalyzed photoinduced strategy that enables direct aromatic C(sp²) H amination alkylarenes using N-hydroxyphthalimides (NHPIs) as nitrogen sources. Mechanistic studies reveal in situ formation PhthN O−B(C6F5)3 anion intermediate facilitates an unusual transfer (EnT)-mediated O homolysis, generating phthalimidyl radical (PhthN•) while regenerating borane catalyst. This method overrides conventional preference for benzylic C oxidation, achieving exclusive with broad substrate scope, including electron-rich/poor alkylarenes, heteroarenes, biomolecules. protocol operates under mild conditions, avoids organic auxiliaries/activators, produces H₂O sole byproduct, thus, making it promising option supplant existing strategies arene amination. Applications in late-stage functionalization pharmaceuticals synthesis nilotinib precursor highlight its synthetic utility. study establishes B(C6F5)3 versatile oxygen atom (OAT) reagent photochemistry, opening avenues sustainable generation.

Language: Английский

Citations

0
Organic N-hydroxyphthalimide catalyzes the selective aerobic oxidation of hydrocarbons promoted by the nonionic surfactants through hydrogen bonding effect DOI

Xiaorui Zhang,

Fengkuan Ma,

Kui Jin

et al.

Molecular Catalysis, Journal Year: 2025, Volume and Issue: 580, P. 115110 - 115110

Published: April 16, 2025

Language: Английский

Citations

0
N‐Oxyl Radicals in Oxidative C–O Coupling: Free‐Radical Hydrogen Substitution and Addition to C=C Bonds DOI
Elena R. Lopat’eva, Igor B. Krylov, Bing Yu

et al.

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 18, 2024

Abstract N ‐oxyl radicals occupy an important place in free‐radical oxidative CH‐functionalization being one of the most efficient redox‐organocatalysts for hydrogen atom abstraction (HAT). Their applications include aerobic radical chain autoxidation, with formation carbon‐carbon and carbon‐heteroatom bonds. The persistent nature N‐ oxyl combined their high reactivity HAT results unique dual chemistry: same can both propagate reaction (at low concentrations) effectively “terminate” carbon‐centered higher concentrations). latter case opens a new synthetic application area radicals, which they act as abstracting species O‐reagents cross‐coupling thus produced. Apart from C−H bond cleavage, reactive have been extensively used recently C=C double functionalization via addition reactions. In this review, reactions introduction fragments alkene difunctionalizations by oxyls are covered emphasis on relationship between conditions selectivity.

Language: Английский

Citations

0