Transition Metal-Catalyzed C–C Bond Formation Reactions Using Alkyl Halides

Abstract

This account reviews transition metal-catalyzed C-C bond formation reactions using alkyl halides, which have rarely been used as carbon sources in conventional transition metal-catalyzed systems. In the reactions, ate complexes formed by the reaction of transition metals with a Grignard reagent play important roles as the active catalytic species. The reactions mentioned here are mechanistically new and provide a promising methodology for the construction of carbon frameworks employing alkyl halides.

Advances in Transition Metal (Pd,Ni,Fe)-Catalyzed Cross-Coupling Reactions Using Alkyl-organometallics as Reaction Partners

“…Thus, it was not until 2002, almost 30 years after the initial report of the Kumada-Corriu coupling, that the first successful Ni-catalyzed C(sp 3 )-C(sp 3 ) coupling reaction was reported by Kambe and coworkers (Figure 100). 118,347,362…”

Nickel Complexes of a Pincer Amidobis(amine) Ligand: Synthesis, Structure, and Activity in Stoichiometric and Catalytic CC Bond‐Forming Reactions of Alkyl Halides

“…Kambe and co-workers postulated a nonradical and formal Ni II /Ni IV mechanism for Ni-catalyzed Kumada-CorriuTamao coupling in the presence of 1,3-butadiene additives. [7,8] Vicic, Phillips, Cµrdenas, and their co-workers reported experimental and theoretical support for a radical-initiated Ni I /Ni III catalytic cycle in Negishi alkyl-alkyl coupling catalyzed by Ni terpyridyl complexes. [12][13][14]19] The reaction pathways for Ni-catalyzed C-C coupling are therefore diverse.…”

“…[5] 2) If oxidative addition occurs, the resulting metal alkyl species can undergo unproductive b-H elimination, which is often both thermodynamically and kinetically favorable. Recent work by Knochel et al, [6] Kambe et al, [7,8] Fu et al, [9][10][11] Vicic et al, [12,13] Cµrdenas et al, [14] Van Koten et al, [15] Cahiez et al, [16] Nakamura et al, [17] and Martin and . In all complexes, the Me NN 2 ligand coordinates to the Ni II ion in a mer fashion, and the square-planar coordination sphere of the metal is completed by an additional donor.…”

Formation of CC and CN Bonds in NiII Ketimide Complexes via Transient NiIII Aryl Imides

“…[1][2][3][4][5] To these ends, the chemistry of early-metal amides [6][7][8][9][10][11] has been explored extensively. The corresponding chemistry of latetransition-metal imido ligands has drawn much less attention.…”