Selenophilicity of Copper in Selenium-Carbon Bond Formation from Selenous Acid Using Cu(II)/Sn(II) Reagent

A selenium transfer reaction from selenous acid to benzyl and alkyl halides is initiated in the presence of stannous chloride and a catalytic amount of cupric chloride resulting in the formation of the corresponding diorganoselenides and/or diorganodiselenides as the major products as indicated by 1H, 13C, 77Se NMR, and MS. The reaction is characterized by a dual-metal effect at the selenium activation and transfer step. Thus, initial reaction of stannous chloride, cupric chloride, and selenous acid gives rise to -Cu2Se. Selenium transfer from the latter to the organic halide takes place with additional assistance of stannous chloride.