A homocoupling method for organohalides and organosulfonates promoted by samarium metal and HMPA, and catalyzed by NiCl has been developed. Various organohalides (benzyl, aryl, heterocyclic, alkenyl and alkyl halides), α-haloacetophenones, and phenyl organosulfonates were tolerated, and the reaction afforded coupling products with high efficiency. Excellent chemoselectivity was exhibited between halides and other groups, such as -COOH, -NO , halogen, heterocyclic ring, ester, and ketone groups. The stereoselectivity suggested that the reaction mechanism might involve an organosamarium species.

The Grignard-type additions were readily achieved under the mediation of CuI (10 mol %) and samarium (2 equiv.) employing various organohalides, e.g. benzyl, aryl, heterocyclic and aliphatic halides (Cl, Br...

By virtue of the reductive coupling reactivity of samarium, cuprous chloride can effectively catalyze the homocoupling of alkylhalides, including the Csp 3

A novel three-component reaction was developed via a one-pot strategy for the construction of diarylmethanol esters by using a halobenzene and an ester in N,N-dimethylformamide (DMF) under mild conditions. The reaction involves the direct functionalization of halobenzene under the Sm−CuI catalyst system. It was proved that 10% (mol) of CuI is sufficient to realize the reductive coupling reaction. Influences of substituents were illustrated from both electronic and steric effects. The reaction mechanism was also discussed.