Visible Light‐Induced EDA‐Complex Triggered Annulative Difunctionalization via Olefin‐Olefin Coupling and Radical Truce‐Smiles Rearrangement

Abstract

AbstractAn EDA complex comprising N‐allyl bromodifluoroacetamides and tertiary alkyl amine was exploited to facilitate annulative difunctionalization reaction under visible‐light irradiation. This external photocatalyst‐free methodology garners olefin‐olefin coupling featuring a radical Truce‐Smiles rearrangement and produced long‐chain functionalized gem‐difluoropyrrolidones from N‐substituted methacryloyl sulfonamides, while simple N‐aryl methacrylamides furnished pyrrolidinone‐oxindole hybrid lactams in high yields. Mechanistic investigations substantiate a combined reaction mechanism, involving charge‐transfer EDA complex‐based radical cascade, alongside an α‐aminoalkyl radical‐triggered XAT process, exhibiting a quantum yield value of 1.48.