Addition Reaction of Polychloro Compounds to Carbon-Carbon Multiple Bonds Catalyzed by Semiconductor Particles under Photoirradiation

Article abstract of DOI:10.1021/jo00085a013

Polychloro compounds were added to olefins in the presence of semiconductor particles (TiO2 or CdS) under photoirradiation.The photoreaction without semiconductors afforded no adducts at all; however, loading of TiO2 with Ag, Cu, or Fe3O4 enhanced the yield of the photoaddition reaction even further.Semiconductors operate as catalysts for the one-electron injection into the polychloro compounds.The relative adsorptions of the polychloro compounds onto the semiconductor particles correlate with the yields of the adducts, while the half-wave reduction potentials of the polychlorides do not.This semiconductor-catalyzed reaction was selective to unfunctionalized olefins and to those bearing a functional group at a remote position.An alkyne furnished the product via further reduction following addition, i.e., 1,1,3-trichloro-1-heptene (7) from 1-hexyne and carbon tetrachloride.