The copper-catalyzed stereoselective defluorinative borylation and silylation of gem-difluoroalkenes was developed. The protocol led to the exclusive formation of Z type monofluoroalkenyl borons and silanes in generally good efficiency with broad substrate scope. The products formed could be readily transformed to other Fcontaining molecules by taking advantage of the versatile reactivities of CÀB and CÀSi bonds. Experimental and theoretical mechanistic studies were conducted which support an olefin insertion/ syn-planar b-F elimination pathway.

A reductive cross-coupling of gem-difluoroalkenes with diverse unactivated and heteroatom substituted olefins through a Fe-catalyzed hydrogen atom transfer (HAT) strategy is reported. Different from the previous HAT-type olefin cross-coupling reactions, the presence of a fluorine atom in the molecule results in a stereoselective β-F cleavage, leading to a C(sp)-C(sp) bond formation. A wide variety of alkylated monofluoroalkenes were obtained in good efficiency with excellent Z selectivity under air- and water-tolerant reaction conditions. A similar defluorinative coupling reaction of monofluoroalkenes was also realized.

A novel synthesis of α-CF3 and α-CF2H amines via the aminofluorination of gem-difluoroalkenes and mono-fluoroalkenes, respectively, is reported. The method employs Selectfluor as an electrophilic fluorine source and acetonitrile as a nitrogen source. Mechanistic studies revealed a single-electron oxidation/fluorine-abstraction/Ritter-type amination pathway. The protocol allowed the synthesis of a broad range of fluorinated amines including those bearing quaternary carbon centers with good efficiency and functional group tolerance.

α‐Haloboronates are useful organic synthons that can be converted to a diverse array of α‐substituted alkyl borons. Methods to α‐haloboronates are limiting and often suffer from harsh reaction conditions. Reported herein is a photochemical radical C‐H halogenation of benzyl N‐methyliminodiacetyl (MIDA) boronates. Fluorination, chlorination, and bromination reactions were effective by using this protocol. Upon reaction with different nucleophiles, the C−Br bond in the brominated product could be readily transformed to a series of C−C, C−O, C−N, C−S, C−P, and C−I bonds, some of which are difficult to forge with α‐halo sp2‐B boronate esters. An activation effect of B(MIDA) moiety was found.

A switchable stereoselectivity in the halohydroxylation of alkenyl MIDA boronates was found. C–B(MIDA) bond hyperconjugation plays the key role.