29681-56-9Relevant 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.
Versatile method for introduction of bulky substituents to alkoxychlorosilanes
Masaoka, Shin,Banno, Tadashi,Ishikawa, Mitsuo
, p. 182 - 192 (2007/10/03)
The reactions of various alkoxytrichlorosilanes prepared in situ from tetrachlorosilane and alcohols, with Grignard reagents bearing a bulky substituent such as the isopropyl, sec-butyl, and cyclohexyl group afforded triisopropyl-, tri(sec-butyl)-, and tricyclohexylalkoxysilane in high yields. The reactions of n-butoxytrichlorosilane with these Grignard reagents produced triisopropyl-, tri(sec-butyl)-, and tricyclohexyl(n-butoxy)silane in 94%, 96%, and 92% yields, respectively. Methoxymethyldichlorosilane reacted with the same Grignard reagents to give diisopropyl-, di(sec-butyl)-, and dicyclohexylmethoxymethylsilane in 84%, 83%, and 83% yields. Treatment of methoxydimethylchlorosilane with the Grignard reagents readily afforded isopropyl-, sec-butyl-, and cyclohexylmethoxydimethylsilane in excellent yields. Similar treatment of methoxydimethylchlorosilane with tert-butylmagnesium chloride gave tert-butylmethoxydimethylsilane in 62% yield.
