Atom transfer radical addition (ATRA) of carbon tetrachloride and chlorinated esters to various olefins catalyzed by Cp′Ru(PPh _3)(PR _3)Cl complexes

摘要

C ~pRu(PPh _3)(PR _3)Cl complexes, where PR _3 = PMe _3, PPh _3, or PTA (PTA = 1,3,5-triaza-7-phosphaadamantane), were used to catalyze the atom transfer radical addition of chlorinated esters (CCl _3CO _2Et, CH _2ClCO _2Et) to styrene, and that of CCl _4 to a variety of olefins. The monoadducts were obtained in moderate to excellent yields. Moreover, high selectivities were obtained for the addition of CCl _4 to internal olefins. The activity of C pRu(PTA)(PPh _3)Cl and C pRu(PTA)(PMe _3)Cl were comparable to that of the highly efficient ATRA catalyst, C ~pRu(PPh _3) _2Cl. The addition of CCl _3CO _2Et to styrene catalyzed by Cp′Ru(PPh _3)(PR _3)Cl (Cp′ = Dp, Ind, Cp, Tp) are also reported here. Two new compounds, 3-chloro-3-phenyl-2-(trichloromethyl)-1-phenylpropan-1-one and 1,3,3,3-tetrachloro-1,2-diphenylpropane, resulting from the addition of CCl _4 to chalcone and cis-stilbene have been isolated and characterized by NMR spectroscopy and X-ray crystallography.