Metal-free hypervalent iodine-promoted tandem carbonyl migration and unactivated C(Ph)–C(Alkyl) bond cleavage for quinolone scaffold synthesis

Abstract

An unexpected iodine(III)-mediated C(sp³)–C(sp²) bond cleavage of 3-(methylamino)-2-(2-substitutedbenzoyl)acrylates for efficient synthesis of privileged scaffold 4-quinolones was described. Notably, a wide range of alkyl groups (e.g. methyl, tert-butyl or alkyl chain) can be conveniently cleaved in this system. The detailed mechanism studies revealed that the transformation proceeded through cascade ipso-cyclization and 1,2-carbonyl migration, the smaller bond energy determined ortho C–C bond cleavage rather than C–H bond cleavage, via an enamine radical intermediate.