2 research outputs found
Light-Induced Alkylation of (Hetero)aromatic Nitriles in a Transition-Metal-Free C–C-Bond Metathesis
A light-induced
C–C-σ-bond metathesis was achieved
through transition-metal-free activation of an unstrained CÂ(sp<sup>3</sup>)–CÂ(sp<sup>3</sup>)-σ-bond in 1-benzyl-1,2,3,4-tetrahydroÂisoÂquinolines.
A photoredox-mediated single-electron oxidation of these precursor
amines yield radical cations which undergo a homolytic cleavage of
a CÂ(sp<sup>3</sup>)–CÂ(sp<sup>3</sup>)-σ-bond rather than
the well-known α-C–H-scission. The resulting carbon-centered
radicals are used in the <i>ipso</i>-substitution of (hetero)Âaromatic
nitriles proceeding through another single-electron transfer-mediated
C–C-bond cleavage and formation
Transition-Metal-Free Decarboxylative Photoredox Coupling of Carboxylic Acids and Alcohols with Aromatic Nitriles
A transition-metal-free
protocol for the redox-neutral light-induced
decarboxylative coupling of carboxylic acids with (hetero)Âaromatic
nitriles at ambient temperature is presented. A broad scope of acids
and nitriles is accepted, and alcohols can be coupled in a similar
fashion through their oxalate half esters. Various inexpensive sources
of UV light and even sunlight can be used to achieve this C–C
bond formation proceeding through a free radical mechanism