Photocatalytic, α-Aminoalkyl Radical-Mediated, Methylene-Extrusive Ring-Closing Transformation of <i>o</i>-Alkynyl and <i>o</i>-Cyano Acrylamides
Ganesh Chandra Upreti, Tavinder Singh, Kirti Khanna, Debasish Sahoo, Anand Singh
Abstract
Herein we report a visible-light-induced, α-aminoalkyl radical-mediated cascade reaction of 1,7-enynes that establishes a unique ring-closing enyne transformation pathway which occurs with concomitant loss of a methylene moiety. The α-aminoalkyl radical derived from N, N -dimethylaniline was demonstrated to be a traceless promoter of enyne reorganization leading to 4-alkylquinolinones. The reaction can also be extended to nitrile-substituted acrylamide systems, leading to carbostyrils. Experiments with deuterated N, N -dimethylaniline- d 6 (PhN(CD 3 ) 2 ) established the involvement of 1,5-H atom transfer in the mechanism.
Topics & Concepts
ChemistryExtrusiveClosing (real estate)MethylenePhotocatalysisRing (chemistry)Transformation (genetics)Medicinal chemistryPhotochemistryStereochemistryCombinatorial chemistryOrganic chemistryCatalysisBiochemistryBusinessGeochemistryGeologyGeneBasaltFinanceRadical Photochemical ReactionsCatalytic C–H Functionalization MethodsSulfur-Based Synthesis Techniques