We report a simple protocol for the photochemical Giese addition of C(sp 3 )-centered radicals to a variety of electron-poor olefins. The chemistry does not require external photoredox catalysts. Instead, it harnesses the excited-state reactivity of 4-alkyl-1,4-dihydropyridines (4-alkyl-DHPs) to generate alkyl radicals. Crucial for reactivity is the use of a catalytic amount of Ni(bpy) 32+ (bpy=2,2′-bipyridyl), which acts as an electron mediator to facilitate the redox processes involving fleeting and highly reactive intermediates.
van Leeuwen T., Buzzetti L., Perego L.A., Melchiorre P. (2019). A Redox-Active Nickel Complex that Acts as an Electron Mediator in Photochemical Giese Reactions. ANGEWANDTE CHEMIE. INTERNATIONAL EDITION, 58(15), 4953-4957 [10.1002/anie.201814497].
A Redox-Active Nickel Complex that Acts as an Electron Mediator in Photochemical Giese Reactions
Melchiorre P.
Ultimo
Supervision
2019
Abstract
We report a simple protocol for the photochemical Giese addition of C(sp 3 )-centered radicals to a variety of electron-poor olefins. The chemistry does not require external photoredox catalysts. Instead, it harnesses the excited-state reactivity of 4-alkyl-1,4-dihydropyridines (4-alkyl-DHPs) to generate alkyl radicals. Crucial for reactivity is the use of a catalytic amount of Ni(bpy) 32+ (bpy=2,2′-bipyridyl), which acts as an electron mediator to facilitate the redox processes involving fleeting and highly reactive intermediates.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
