Zirconium-redox-shuttled cross-electrophile coupling of aromatic and heteroaromatic halides

C(sp2)–C(sp2) Reductive Cross-Coupling of Triarylphosphines with Aryl Halides by Palladium/Nickel Co-catalysis

“…Transition metal-catalyzed C­(sp 2 )–C­(sp 2 ) reductive cross-coupling reactions of two aryl electrophiles have received a great deal of attention as some of the most efficient methods for the synthesis of biaryls due to the wide availability of electrophiles and because the reactions circumvent the tedious preparation of organometallic reagents . To date, various aryl halides and O-based aryl electrophiles have been utilized in such transformations. In recent years, sporadic examples of C­(Ar 1 )–C­(Ar 2 ) reductive cross-coupling involving aryl amine derivatives, , pyridyl sulfone, and aryl nitriles have also been reported.…”

Simultaneous Denitrative C–C Bond Formation and Construction of Pyrazole Ring Leading to 1,1'-Diphenyl-4,4'-bipyrazole

“…7 Accordingly, numerous synthetic methods have been reported. 5,[7][8][9][10] The main methods include transition-metal-catalyzed coupling reaction 5,8 and halogenating reagent-promoted coupling reaction of pyrazoles, 9 or construction of pyrazole rings using polyfunctionalized substrate. 10 To the contrary, the present reaction includes a construction of pyrazole ring and a coupling reaction accompanied by denitrative C-C bond formation under neutral conditions, which is a hitherto unknown reaction type.…”

Mechanistic views and computational studies on transition-metal-catalyzed reductive coupling reactions

“…1, the concerted oxidative addition of iodobenzene to the Pd 0 catalyst proceeds via transition state TS1 to generate the Pd II complex with the readily attainable free energy of activation (16.5 kcal mol À1 ). 105 Bromobenzene reacts with the Pd 0 catalyst via TS2 with an energy barrier of 25.6 kcal mol À1 . DFT calculations were performed in the group of Gosmini and Gandon to gain mechanistic insights into the activation of the C(sp 2 )-CN bond by cobalt complexes (Fig.…”

“…The different chemoselectivity can be effectively tuned by appropriate transition metal catalysts, which are capable of identifying the subtle steric and electronic differences between two intrinsically similar coupling partners. 53,105,[142][143][144] Through a series of DFT investigations, Guan and Su's group investigated the selective reductive coupling of bromobenzene and 4methoxyphenyltriflate via Ni/Pd dual catalysis (Fig. 20).…”