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...

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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
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container_issue 17
container_start_page 3652
container_title Organic letters
container_volume 26
creator Upreti, Ganesh Chandra
Singh, Tavinder
Khanna, Kirti
Sahoo, Debasish
Singh, Anand
description 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.
doi_str_mv 10.1021/acs.orglett.4c01165
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title Photocatalytic, α‑Aminoalkyl Radical-Mediated, Methylene-Extrusive Ring-Closing Transformation of o‑Alkynyl and o‑Cyano Acrylamides
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