A highly versatile and efficient method has been developed for the Barbier-Grignard-type arylation and alkylation of aldehydes using unactivated bromides and Mg in tetrahydrofuran at 65 ℃ promoted by BiCl 3 and PPh 3. This method has offered high yields of 61%～99% mostly, mild reaction conditions, short reaction time, easy workup and a one-pot procedure. The steric, electronic effects and some new results have been discussed. A possible mechanism catalyzed by BiCl 3 and Ph 3 P was reasonably proposed.

Carried out in THF-toluene at 103 ℃, the first one-pot Barbier-Grignard reaction to synthesize tertiary alcohols has been developed and systematically investigated using aromatic acids and unactivated aryl bromides in the presence of 10 mol% of Ta 2 O 5. A wide range of substituted tertiary alcohols were obtained in moderate to good yields of 48%～87%. Steric and electronic effects of reactants on the reaction have been discussed. A possible mechanism catalyzed by Ta 2 O 5 is proposed.