Harada Toshiro, Kutsuwa Emiko
Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan.
J Org Chem. 2003 Aug 22;68(17):6716-9. doi: 10.1021/jo034743p.
Treatment of allenic zinc reagents (R(1)R(2)C[double bond]C[double bond]C(R(3))ZnL), generated by the reaction of propargyl derivative (R(1)R(2)C(X)triple bond with triorganozincates (R(3)(3)ZnLi), under oxygen atmosphere in the presence of ZnCl(2) and chlorotrimethylsilane afforded propargyl hydroperoxides (R(1)R(2)C(OOH)C[triple bond];CR(3)) regioselectively. In this reaction, the use of ZnCl(2) and chlorotrimethylsilane as additives is essential for the transformation of the initially generated allenic reagents to more reactive chlorozinc species.
