Reaction of Olefins with a Mixture of Phenylselenenyl Chloride and Mercury(II) Thiocyanate. Selective Syntheses of β-(Phenylseleno)alkyl Isothiocyanates as Precursors of Vinylic Isothiocyanates

Article abstract of DOI:10.1021/jo00174a018

The reaction of olefins with a mixture of phenylselenenyl chloride and mercury(II) thiocyanate in benzene as the solvent affords β-(phenylseleno)alkyl isothiocyanates selectively in good to excellent yields.The mercury salt not only increases the N selectivity in a kinetically controlled reaction but also accelerates the isomerization of β-(phenylseleno)alkyl thiocyanates to the corresponding isothiocyanates.Oxidative elimination of the β-(phenylseleno)alkyl isothiocyanates gives predominantly vinylic isothiocyanates together with a small amount of allylic isothiocyanate s.This sequence constitutes a convenient method for conversion of olefins to vinylic isothiocyanates.