Thermal reaction of cyclic alkadiene with trichlorosilane. Preparative and mechanistic aspects

The thermal reactions of trichlorosilane (1a) with cyclic alkadienes such as cyclopentadiene (2a), 1,3-cyclohexadiene (2b), and 1,4-cyclohexadiene (2c) were studied at temperatures ranging from 170 °C to 250 °C. In this reaction, the hydrosilylation rate increased as the reaction temperature was raised using an equimolar ratio of 1a to 2a. The reaction of 2a with 1a at 250 °C afforded 2-cyclopentenyltrichlorosilane (3a) as the major hydrosilylation product within 1 h in good yield (82%). This reaction also works when dicyclopentadiene (2a′) was used as a reactant instead of 2a. In a large scale preparation under the same conditions, 3a was obtained in 82% isolated yield. It is significant to note that 2a′ can be used for the hydrosilylation, with no requirement of a cracking step under our thermal conditions. While the reaction of cyclohexadienes with 1a under the same conditions gave a mixture of three hydrosilylation products such as 2-cyclohexenyltrichlorosilane (3b), 3-cyclohexenyltrichlorosilane (3c) and cyclohexyltrichlorosilane (5) in moderate yields, along with other unsaturated C6 components, such as benzene and cyclohexene. In the thermal reaction of cycloalkadienes with 1a, the five-membered-ring diene 2a undergoes both a hydrosilylation reaction with 1a as well as a [4 + 2] cycloaddition reaction, leading to the hydrosilylation product 3a in good yield. While the six-membered ring dienes, 2b and 2c, undergo four different types of reactions, including hydrosilylation, [4 + 2] cycloaddition, dehydrogenation, and hydrogenation in competition to give the hydrosilylation products, hexane, and benzene, respectively. The reaction rates of cyclic alkadienes under our thermal conditions increase in the following order: 2c << 2b < 2a.

The thermal reaction of cyclopentadiene (or dicyclopentadiene) with trichlorosilane (1a) at 250 °C gave cyclopent-2-enyltrichlorosilane as a major product in good 82% yield. While the similar reaction of 1,3-cyclohexadiene with 1a afforded the 16: 1 mixture of 2- and 3-cyclohexenyltrichlorosilane in 68%yield along with benzene (11%) and cyclohexene (9%).Figure optionsDownload as PowerPoint slideHighlights
► Thermal hydrosilylation of cycloalkadienes with trichlorosilane.
► The ring-size effect of cycloalkadienes in the thermal hydrosilylation with trichlorosilane.
► The double bond conjugation effect on cyclohexadiene.