Masayuki Kameyama

Palladium-catalyzed reaction of 1-aza-5-germa-5-organobicyclo[3.3.3]undecane with aryl bromide

Abstract Successive treatment of triallylamine with zirconocene chloride hydride and germanium tetrachloride affords 1-aza-5-germa-5-chlorobicyclo[3.3.3]undecane, which is converted to the 5-organo derivatives by the reaction with Grignard or lithium reagents. The organo groups showed higher reactivities toward Stille-type coupling than the corresponding organotributylgermanes.

Palladium-catalyzed carbostannylation by means of reagents containing carbon–tin–halogen inter-element linkages

Reagents containing carbon–tin–halogen inter-element linkages were effective for palladium-catalyzed carbostannylation. In situ generated allyltin trichlorides add to carbon–carbon double bonds of bicyclo[2.2.1]hept-2-ene (norbornene) and bicyclo[2.2.1]hepta-2,5-diene (norbornadiene), stereoselectively, under the catalysis of palladium(0) species in good yields. The regioselectivity of unsymmetrically substituted allylic reagents dramatically alters with the choice of the tin(II) salt. Aryltin trichlorides undergo palladium-catalyzed arylstannylation of norbornene, giving a mixture of products composed of that taking one norbornene and that taking two norbornenes. The product ratio is dependent on the choice of the solvent and electronic nature of the aromatic substituent.

Reactions of azo and azoxy sulphones with transition metal complexes. Part 7. Arylation of olefins with arylazoxy aryl sulphones catalysed by a palladium(0) phosphine complex

The arylation of acyclic and cyclic olefins by arylazoxy aryl sulphones has been investigated in the presence of a palladium(0) catalyst in benzene. Both of the aryl groups of the arylazoxy aryl sulphones are found to participate in the arylation. Two equivalents of aryl-substituted olefins were obtained when the reactions were carried out at 80 °C, whereas one equivalent of olefin was arylated at 120 °C. A plausible catalytic cycle involving a diarylpalladium(II) species is proposed.