Contra-thermodynamic Olefin Isomerization by Chain-Walking Hydrofunctionalization and Formal Retro-hydrofunctionalization
We report a contra-thermodynamic isomerization of internal olefins to terminal olefins driven by redox reactions and formation of Si-F bonds. This process involves chain-walking hydrosilylation of internal olefins and subsequent formal retro-hydrosilylation. The process rests upon the high activities of platinum hydrosilylation catalysts for isomerization of metal alkyl intermediates and a new, metal-free process for the conversion of alkylsilanes to alkenes. By this approach, 1,2-disubstituted and trisubstituted olefins are converted to terminal olefins.
Hanna, Steven,Butcher, Trevor W.,Hartwig, John F.
supporting information
p. 7129 - 7133
(2019/09/12)
Hydrosilylation of cyclohexene, 1-methylcyclohexene, and isopropylidenecyclohexane
Hydrosilylation of cyclohexene and isopropylidenecyclohexane with chloro(methyl)silanes Me3-n SiHCln (n = 1-3) gives rise to cyclohexyl- and chloro(2-cyclohexylpropyl)methylsilanes. Hydrosilylation of 1-methylcyclohexene with chlorodimethylsilane (n = 1) occurs anomalously and involves double-bond migration to form a mixture of seven compounds: the cis and trans isomers of 2-, 3-, 4-chlorodimethyl(methylcyclohexyl)silanes and chlorodimethyl(cyclohexylmethyl)silane. Chlorodimethylsilane (n = 2) adds to 1-methylcyclohexene to form a mixture of the cis and trans isomers of dichloro(methyl)(2-methylcyclohexyl)silane and dichloro(cyclohexylmethyl) methylsilane. With trichlorosilane (n = 3), no other products than trichloro(cyclohexylmethyl)silane are formed. The hydrosilylation products were reacted with ethynylmagnesium bromide to synthesize the corresponding ethynyl derivatives. 2004 MAIK "Nauka/Interperiodica".
Yarosh,Zhilitskaya,Yarosh,Albanov,Voronkov
p. 1895 - 1899
(2007/10/03)
More Articles about upstream products of 18388-16-4