Litcius/Paper detail

(Fluoro)alkylation of alkenes promoted by photolysis of alkylzirconocenes

Xiaoxiao Ren, Xing Gao, Qiao‐Qiao Min, Shu Zhang, Xingang Zhang

2022Chemical Science32 citationsDOIOpen Access PDF

Abstract

) group into an aliphatic chain at the desired position remains challenging. Here, we report an unprecedented example of alkylzirconocene promoted difluoroalkylation of alkyl- and silyl-alkenes with a variety of unactivated difluoroalkyl iodides and bromides under the irradiation of visible light without a catalyst. The resulting difluoroalkylated compounds can serve as versatile synthons in organic synthesis. The reaction can also be applied to activated difluoroalkyl, trifluoromethyl, perfluoroalkyl, monofluoroalkyl, and nonfluorinated alkyl halides, providing a general method to controllably access fluorinated compounds. Preliminary mechanistic studies reveal that a single electron transfer (SET) pathway induced by a Zr(iii) species is involved in the reaction, in which the Zr(iii) species is generated by the photolysis of alkylzirconocene with blue light.

Topics & Concepts

AlkylationChemistrySynthonAlkylTrifluoromethylSilylationPhotodissociationHalideCombinatorial chemistryCatalysisPhotochemistryOrganic chemistryFluorine in Organic ChemistryRadical Photochemical ReactionsInorganic Fluorides and Related Compounds