Four-component radical-dual-difunctionalization (RDD) and decarbonylative alkylative peroxidation of two different alkenes with aliphatic aldehydes and TBHP
From difunctionalization of a single alkene to radical-dual-difunctionalization of two different alkenes! Abundant aliphatic aldehydes were readily decarbonylated into alkyl radicals for the cascade construction of C(sp3)-C(sp3), C(sp3)-C(sp3) and C(sp3)-O bonds via double radical addition and radical-radical coupling, following the intrinsic nucleophilic/electrophilic reactivity of both the radicals and alkenes.
Fe-Catalyzed decarbonylative alkylation-peroxidation of alkenes with aliphatic aldehydes and hydroperoxide under mild conditions
A convenient Fe-catalyzed decarbonylative alkylation-peroxidation of alkenes with aliphatic aldehydes and TBHP to provide chain elongated peroxides is developed, which is further applied to the one-pot synthesis of alkylated ketones. Aliphatic aldehydes were decarbonylated into 1°, 2° and 3° alkyl radicals at low temperature which subsequently allows the cascade construction of C(sp3)-C(sp3) and C(sp3)-O bonds via radical insertion and radical-radical coupling. Various alkenes including mono-substituted, terminally disubstituted or internally disubstituted styrenes bearing synthetically useful functional groups and electron-poor acrylates were tolerated.
Wu, Chuan-Shuo,Li, Rong,Wang, Qi-Qiang,Yang, Luo
supporting information
p. 269 - 274
(2019/01/28)
Iron-catalyzed carbonylation-peroxidation of alkenes with aldehydes and hydroperoxides
A three-component reaction of alkenes, aldehydes, and hydroperoxides catalyzed by FeCl2 to β-peroxy ketones has been achieved. This three-component reaction can be also applied to the synthesis of α-carbonyl epoxides, through either a stepwise base-induced epoxidation of the separated β-peroxy ketone products or a one-pot process by simply adding base to the reaction mixture after the completion of the three-component reaction.