Long-chain hydrocarbons carrying vinyl groups, chlorine atoms or oxygen functions at the terminal positions can be prepd. with excellent yields by copper mediated coupling of alkyl tosylates and Grignard reagents. E.g., Li2CuCl4 catalyzed the coupling of CH2:CH(CH2)3MgBr with TsO(CH2)nOTs (Ts = p-MeC6H4SO2; n = 5-9) to give CH2:CH(CH2)n+6CH:CH2. Li2CuCl3 catalyzed the coupling of Cl(CH2)6OTs with BrMg(CH2)nMgBr (n = 5, 6, 8) to give good yields of Cl(CH2)n+12Cl. No breeding stage is necessary if the cuprous complex dilithium trichlorocuprate rather than a cupric salt is employed as the catalyst. [on SciFinder (R)]