Cross‐Electrophile Coupling

Ni(I)–Alkyl Complexes Bearing Phenanthroline Ligands: Experimental Evidence for CO2 Insertion at Ni(I) Centers

“…Although nickel catalysts supported by (di)­phosphine or N-heterocyclic carbene ligands are routinely employed in a myriad of Ni-catalyzed C–C and C–heteroatom bond-forming reactions, only finely tuned 1,10-phenanthroline derivativesphen ligandshave enabled the carboxylation of unactivated alkyl electrophiles either at the initial C­(sp 3 )–X site or at remote C­(sp 3 )–H bonds via chain-walking of the Ni catalyst along the alkyl side chain (Scheme ). , Furthermore, a careful analysis of the literature indicates that phen ligands are also crucial for a wide number of Ni-catalyzed cross-couplings of unactivated alkyl halides, indicating that the importance of these ligands extends beyond carboxylation reactions. , …”

Recent synthetic methods involving carbon radicals generated by electrochemical catalysis

“…41,42 The relatively inertness and high BDEs of the unactivated C(sp 2 )–Cl bonds make their application in reductive cross-coupling a synthetic challenge. 43,44 Due to their high reduction potentials (<−2.2 V vs . Fc/Fc + ), which lie at or beyond the reduction limits of conventional visible-light photoredox catalysts, aryl chloride substrates are often overlooked in electroreductive and photoreductive chemistry.…”

Photoredox/Nickel Dual Catalysis Enables the Synthesis of Alkyl Cyclopropanes via C(sp3)–C(sp3) Cross Electrophile Coupling of Unactivated Alkyl Electrophiles

“…Cross-electrophile coupling (XEC) reaction is an intriguing strategy for constructing C–C bonds under mild conditions . The field has been advanced with activated electrophiles or substrates having different oxidative addition rates to favor cross-selectivity . However, the coupling between two unactivated substrates with the same reactivity is challenging .…”