1432-40-2Relevant 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.
Intermolecular Dehydrogenative C?H/Si?H Cross-Coupling for the Synthesis of Arylbenzyl Bis(silanes)
He, Chuan,You, Lijun,Yuan, Wei
supporting information, p. 3079 - 3082 (2021/07/22)
An iridium-catalyzed intermolecular dehydrogenative C?H/Si?H cross-coupling reaction for the synthesis of arylbenzyl bis(silanes) is developed. This hydrosilyl group steered intermolecular C?H silylation process features high chemo- and regioselectivity,
Mechanistic Study of Arylsilane Oxidation through 19F NMR Spectroscopy
Rayment, Elizabeth J.,Mekareeya, Aroonroj,Summerhill, Nick,Anderson, Edward A.
supporting information, p. 6138 - 6145 (2017/05/09)
The mechanism of the oxidation of arylsilanes to phenols has been investigated using19F NMR spectroscopy. The formation of silanols in these reactions results from a rapid background equilibrium between silanol and alkoxysilane; the relative rates of reaction of these species was evaluated by modeling of concentration profiles obtained through 19F NMR spectroscopic reaction monitoring. Combining these results with a study of initial rates of phenol formation, and of substituent electronic effects, a mechanistic picture involving rapid and reversible formation of a pentavalent peroxide ate complex, prior to rate-limiting aryl migration, has evolved.
Ru(ii)-Pheox-catalyzed Si-H insertion reaction: construction of enantioenriched carbon and silicon centers
Nakagawa, Yoko,Chanthamath, Soda,Fujisawa, Ikuhide,Shibatomi, Kazutaka,Iwasa, Seiji
supporting information, p. 3753 - 3756 (2017/04/03)
We established a highly enantioselective Si-H insertion reaction to construct chiral centers at the carbon and silicon atoms, using a Ru(ii)-pheox catalyst. The catalytic asymmetric Si-H insertion reaction of α-methyl-α-diazoesters proceeded smoothly with excellent stereoinduction at both the neighboring carbon and silicon atoms (up to 99% yield and 99% ee).
Synthesis of phenols via fluoride-free oxidation of arylsilanes and arylmethoxysilanes
Rayment, Elizabeth J.,Summerhill, Nick,Anderson, Edward A.
experimental part, p. 7052 - 7060 (2012/10/07)
Rapid, efficient methods have been developed to prepare phenols from the oxidation of arylhydrosilanes. The effects of arene substituents and fluoride promoters on this process show that while electron-deficient arenes can undergo direct oxidation from the hydrosilane, electron-rich aromatics benefit from silane activation via oxidation to the methoxysilane using homogeneous or heterogeneous transition metal catalysis. The combination of these two oxidations into a streamlined flow procedure involving minimal processing of reaction intermediates is also reported.
