Transition‐Metal‐Catalyzed Carbohalogenative 1,2‐Difunctionalization of C−C Multiple Bonds

Abstract

Transition-metal-catalyzed 1,2-carbohalofunctionalization reactions of CÀ C multiple bonds have emerged rapidly over the past decade as a powerful tool for generating a new carbon-carbon and carbon-halogen bond via transposition of an existing carbon-halogen σ bond. Exploring this highly efficient mode of carbon-carbon multiple bond difunctionalization, various research groups have established novel strategies for the synthesis of organohalides by utilizing wide variety of transition metal catalysts under mild reaction conditions, avoiding stoichiometric waste of by-products, and with improved levels of chemo-, regio-, and stereoselectivities. Most of the 1,2-carbohalo-functionalization reactions involve either the carbon-halogen reductive elimination mechanism or the atom transfer radical addition (ATRA) mechanism. This review summarizes the recent progress in the area of transitionmetal-catalyzed intra-and intermolecular 1,2-carbo-halo-functionalization reactions of carbon-carbon multiple bonds and explicates the underlying potentiality and challenges within the field.

Recent Strategies for Carbon−Halogen Bond Formation Using Nickel

“…The transfer of an aryl halide across a p-system has become an increasingly popular strategy for the generation of vinyl and alkyl halides. [55][56][57] A catalytic method was reported by Lautens and Newman in 2011 using a palladium precatalyst in the presence of bulky phosphine ligands such as QPhos and P(tBu) 3 , followed by a related method reported by Tong using bidentate ligands employing vinyl halides. [58][59][60] Recently, the Tong group reported a novel strategy to induce asymmetric carboiodination and carbobromination reactions enabled by the addition of ammonium salts.…”

Photoredox catalysis in nickel-catalyzed C–H functionalization

“…Nickel-catalyzed alkene 1,2-difunctionalization is considered as useful method for preparing complex molecules in a single-step reaction [137][138][139]. In this aspect, the groups by Kong [140] and Molander [141] independently demonstrated photoredox/nickelcatalyzed approaches to olefin difunctionalizations involving C(sp 3 )-H activation.…”

Recent Strategies for Carbon−Halogen Bond Formation Using Nickel

“…Thet ransfer of an aryl halide across a p-system has become an increasingly popular strategy for the generation of vinyl and alkyl halides. [55][56][57] Acatalytic method was reported by Lautens and Newman in 2011 using ap alladium precatalyst in the presence of bulky phosphine ligands such as QPhos and P(tBu) 3 ,followed by arelated method reported by Tong using bidentate ligands employing vinyl halides. [58][59][60] Recently,t he Tong group reported an ovel strategy to induce asymmetric carboiodination and carbobromination reactions enabled by the addition of ammonium salts.…”