title: Light-Induced Alkylation of (Hetero)aromatic Nitriles in a Transition-Metal-Free C-C-Bond Metathesis.
abstract: A light-induced C-C-σ-bond metathesis was achieved through transition-metal-free activation of an unstrained C(sp3)-C(sp3)-σ-bond in 1-benzyl-1,2,3,4-tetrahydroisoquinolines. A photoredox-mediated single-electron oxidation of these precursor amines yield radical cations which undergo a homolytic cleavage of a C(sp3)-C(sp3)-σ-bond rather than the well-known α-C-H-scission. The resulting carbon-centered radicals are used in the ipso-substitution of (hetero)aromatic nitriles proceeding through another single-electron transfer-mediated C-C-bond cleavage and formation.
authors.affiliation: Institute of Organic Chemistry, University of Mainz , Duesbergweg 10-14, D-55128 Mainz, Germany.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Lipp
authors.affiliation: Institute of Organic Chemistry, University of Mainz , Duesbergweg 10-14, D-55128 Mainz, Germany.
authors.forename: Alexander
authors.initials: A
authors.lastname: Lipp
authors.affiliation: Institute of Organic Chemistry, University of Mainz , Duesbergweg 10-14, D-55128 Mainz, Germany.
authors.forename: Heiner
authors.initials: H
authors.lastname: Detert
authors.affiliation: Institute of Organic Chemistry, University of Mainz , Duesbergweg 10-14, D-55128 Mainz, Germany.
authors.forename: Till
authors.identifier: 0000-0002-3266-4050
authors.initials: T
authors.lastname: Opatz