56-33-7Relevant articles and documents
The cyclopropylmethylsilane terminated prins reaction: Stereoelectronic controlled formation of (E)-skipped dienes
Braddock,Badine,Gottschalk
, p. 1909 - 1912 (2001)
The reaction of 1-phenyldimethylsilylmethyl-2-vinyl cyclopropane with acetals under the influence of TMSOTf proceeds smoothly to provide skipped dienes with exclusive E-olefin geometry regardless of the initial cis/trans configuration of the starting cyclopropane. The reaction is under stereoelectronic control where the intermediate Prins cation formed is stabilised by the adjacent cyclopropane grouping in a bisected conformation before undergoing silyl-directed collapse.
Volumetric and Refractive Properties of the Mixtures of 1,1,3,3-Tetramethyl-1,3-diphenyldisiloxane with Various Organosilicon Compounds at T = (308.15 to 328.15) K
Dong, Hong,Yu, Lijiao,Hu, Yuqian,Wu, Chuan
, p. 1485 - 1495 (2016)
The density and refractive index were determined for four binary mixtures of 1,1,3,3-tetramethyl-1,3-diphenyldisiloxane with 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, and 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane at different temperatures (T = 308.15, 313.15, 318.15 323.15 and 328.15 K) and atmospheric pressure using a DMA4500/RXA170 combined system. The excess molar volume, partial excess volume at infinite dilution, isobaric coefficient of thermal expansion, excess refraction indices, Lorentz-Lorenz molar refraction, and the deviation in molar refraction have been calculated using these data. The results have been incorporated into the Redlich-Kister equation and used to estimate the binary interaction parameters and standard deviation. The values of partial excess volume at infinite dilution and excess refraction indices for the four binary systems at different temperatures were calculated using the adjustable parameters of the Redlich-Kister smoothing equation. The factors that affect these excess quantities have been discussed.
Metal-free hydrogen evolution cross-coupling enabled by synergistic photoredox and polarity reversal catalysis
Cao, Jilei,Lu, Kanghui,Ma, Lishuang,Yang, Xiaona,Zhou, Rong
supporting information, p. 8988 - 8994 (2021/11/23)
A synergistic combination of photoredox and polarity reversal catalysis enabled a hydrogen evolution cross-coupling of silanes with H2O, alcohols, phenols, and silanols, which afforded the corresponding silanols, monosilyl ethers, and disilyl ethers, respectively, in moderate to excellent yields. The dehydrogenative cross-coupling of Si-H and O-H proceeded smoothly with broad substrate scope and good functional group compatibility in the presence of only an organophotocatalyst 4-CzIPN and a thiol HAT catalyst, without the requirement of any metals, external oxidants and proton reductants, which is distinct from the previously reported photocatalytic hydrogen evolution cross-coupling reactions where a proton reduction cocatalyst such as a cobalt complex is generally required. Mechanistically, a silyl cation intermediate is generated to facilitate the cross-coupling reaction, which therefore represents an unprecedented approach for the generation of silyl cationviavisible-light photoredox catalysis.
Hydrosilylative reduction of carbon dioxide by a homoleptic lanthanum aryloxide catalyst with high activity and selectivity
Chang, Kejian,Maron, Laurent,Xu, Xin,Zheng, Xizhou,del Rosal, Iker
supporting information, p. 7804 - 7809 (2021/06/16)
An efficient tandem hydrosilylation of CO2, which uses a combination of a simple, homoleptic lanthanum aryloxide and B(C6F5)3, was performed. Use of a less sterically hindered silane led to an exclusive reduction of CO2to CH4, with a turnover frequency of up to 6000 h?1at room temperature. The catalytic system is robust, and 19?400 turnovers could be achieved with 0.005 mol% loading of lanthanum. The reaction outcome depended highly on the nature of the silane reductant used. Selective production of the formaldehyde equivalent,i.e., bis(silyl)acetal, without over-reduction, was observed when a sterically bulky silane was used. The reaction mechanism was elucidated by stoichiometric reactions and DFT calculations.