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

Abstract An 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.