Photocatalytic, α‑Aminoalkyl Radical-Mediated, Methylene-Extrusive Ring-Closing Transformation of o‑Alkynyl and o‑Cyano Acrylamides

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 demonstra...

Full description

Saved in:
Bibliographic Details
Published in:Organic letters 2024-05, Vol.26 (17), p.3652-3656
Main Authors: Upreti, Ganesh Chandra, Singh, Tavinder, Khanna, Kirti, Sahoo, Debasish, Singh, Anand
Format: Article
Language:English
Citations: Items that this one cites
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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(CD3)2) established the involvement of 1,5-H atom transfer in the mechanism.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.4c01165