145251-34-9Relevant academic research and scientific papers
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.
Photolysis of 1,3-dimesitylhexamethyltrisilane and 1,2-dimesityltetramethyldisilane
Braddock-Wilking, Janet,Chiang, Michael Y.,Gaspar, Peter P.
, p. 197 - 209 (2008/10/08)
Irradiation at 254 nm of solutions containing 1,3-dimesitylhexamethyltrisilane, (MesMe2-Si)2SiMe2, leads to the formation of 1-mesityl-1-methylsilene, MesMeSi=CH2, in addition to the anticipated dimethylsilylene, Me2Si:. The coproduct of dimethylsilylene extrusion, 1,2-dimesityltetramethyldisilane, (MesMe2Si)2, is itself photolabile, producing high yields of mesityldimethylsilane, MesMe2SiH, and 1-mesityl-1-methylsilene. Trapping experiments indicate that both molecular elimination and silicon-silicon bond homolysis followed by disproportionation lead to the silene, whose dimerization yields cis- and trans-1,3-dimesityl-1,3-dimethyl-1,3-disilacyclobutanes. Both the cis- and trans-1,3-disilacyclobutanes were structurally characterized by X-ray crystallography. The silene can be trapped by a variety of reagents in high yield.
