Visible-light-induced 1,2-alkylarylation of alkenes with a-C(sp3)–H bonds of acetonitriles involving neophyl rearrangement under transition-metal-free conditions

• Published in: Tetrahedron letters 2018-12, Vol.59 (52), p.4551-4556
• Main Authors: Wang, Qiao-Lin, Chen, Zan, Zhou, Cong-Shan, Xiong, Bi-Quan, Zhang, Pan-Liang, Yang, Chang-An, Liu, Yu, Zhou, Quan
• Format: Article
• Language: English
• Subjects: 1,2-Alkylarylation; Acetonitriles; C–H functionalization; Visible light photoredox catalysis; α,α-Diaryl allylic alcohols
• ISSN: 0040-4039; 1873-3581
• DOI: 10.1016/j.tetlet.2018.11.025

[Display omitted] •The 1,2-alkylarylation occurs under transition-metal-free and oxidant-free conditions.•A variety of important 5-oxo-pentanenitriles were obtained.•The results proved that the cleavage of C(sp3)–H bond of acetonitrile is a rate-limiting step. An efficient visible-light-induced difunctionalization of alkenes with a-C(sp3)–H bonds of nitriles is described for the constructing of diverse 5-oxo-pentanenitriles under transition-metal-free conditions. This protocol proceeds via the functionalization of C(sp3)–H bond and radical addition/intramolecular 1,2-aryl migration processes, which features a wide scope of substituted α,α-diaryl allylic alcohols. The results of kinetic isotope experiments show that the cleavage of C(sp3)–H bond of acetonitriles is a rate-limiting step.