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A Redox‐Active Nickel Complex that Acts as an Electron Mediator in Photochemical Giese Reactions
Author(s) -
van Leeuwen Thomas,
Buzzetti Luca,
Perego Luca Alessandro,
Melchiorre Paolo
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201814497
Subject(s) - chemistry , reactivity (psychology) , photochemistry , radical , redox , alkyl , catalysis , reactive intermediate , photoredox catalysis , excited state , nickel , organic chemistry , photocatalysis , medicine , physics , alternative medicine , pathology , nuclear physics
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) 3 2+ (bpy=2,2′‐bipyridyl), which acts as an electron mediator to facilitate the redox processes involving fleeting and highly reactive intermediates.