78133-25-2Relevant academic research and scientific papers
STEREOCHEMISTRY OF REACTION OF (E)- AND (Z)-Β-TRIMETHYLSILYLSTYRENE WITH ARYLPALLADIUM TETRAFLUOROBORATES GENERATED FROM ARENEDIAZONIUM TETRAFLUOROBORATES AND PALLADIUM(0)
Kikukawa, Kiyoshi,Ikenaga, Kazutoshi,Wada, Fumio,Matsuda, Tsutomu
, p. 1337 - 1340 (1983)
(E)- and (Z)-PhCH=CHSiMe3 react easily with +BF4- to give (E)-PhCH=CHAr and Ph(Ar)C=CH2 at 25 deg C.Stereochemistry of the desilylation is disclosed by using (E)- and (Z)-PhCH=CDSiMe3, that is syn-addition of Ar-Pd species followed by anti-elimination of Pd and Me3Si moiety for (E)-isomer and syn-elimination for (Z)-isomer are proposed.
Reaction of Diazonium Salts with Transition Metals. Part 11. Palladium-catalyzed Aryldesilylation of Alkenylsilanes by Arenediazonium Salts
Ikenaga, Kazutoshi,Kikukawa, Kiyoshi,Matsuda, Tsutomu
, p. 1959 - 1964 (2007/10/02)
Under palladium(0) catalysis, both (E)- and (Z)-RCH=CHSiMe3(R=Rh, 4-MeC6H4, 4-NO2C6H4, n-C6H13, and MeOCH2) were easily aryldesilylated by ArN2X(Ar=Ph, 4-MeC6H4, 4-BrC6H4 and 4-NO2C6H4; X=BF4, PF6, and Cl) to give (E)-RCH=CHAr and RC(Ar)=CH2 as the main products at 25 deg C in acetonitrile. anti- and syn-1,2-Elimination of Pd(0) and Me3Si from the adducts, threo- and erythro-RCH(PdX)CHSiMe3, generated from ArPdX and (E) and (Z)-RCH=CHSiMe3, respectively, are proposed for the formation of (E)-RCH=CHAr from either isomer of RCH=CHSiMe3.
Cp2TiCl2-CATALYZED GRIGNARD EXCHANGE REACTIONS WITH ACETYLENES. A CONVENIENT METHOD FOR PREPARATION OF E-ALKENYL GRIGNARD REAGENTS
Sato, Fumie,Ishikawa, Hiroaki,Sato, Masao
, p. 85 - 88 (2007/10/02)
Disubstituted acetylenes react with isobutylmagnesium halide in the presence of a catalytic amount of Cp2TiCl2 in ether to afford E-alkenyl Grignard reagents selectively and in almost quantitative yields.The regiochemistry of this hydromagnesation reaction is high for alkylarylacetylenes and silylacetylenes giving E-ArC(MgBr)=CHR from alkylarylacetylenes, E-ArC(MgBr)=CH(SiMe3) from arylsilylacetylenes, and E-CHR=C(MgBr)(SiMe3) from alkylsilylacetylenes, respectively.Thanks to the high reactivity of the Grignard reagent, the present reaction offers a novel, selective and operationally simple route for preparation of trisubstituted olefins.
