55445-32-4Relevant 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.
Selective Electrochemical Hydrolysis of Hydrosilanes to Silanols via Anodically Generated Silyl Cations
Liang, Hao,Wang, Lu-Jun,Ji, Yun-Xing,Wang, Han,Zhang, Bo
supporting information, p. 1839 - 1844 (2020/12/01)
The first electrochemical hydrolysis of hydrosilanes to silanols under mild and neutral reaction conditions is reported. The practical protocol employs commercially available and cheap NHPI as a hydrogen-atom transfer (HAT) mediator and operates at room temperature with high selectivity, leading to various valuable silanols in moderate to good yields. Notably, this electrochemical method exhibits a broad substrate scope and high functional-group compatibility, and it is applicable to late-stage functionalization of complex molecules. Preliminary mechanistic studies suggest that the reaction appears to proceed through a nucleophilic substitution reaction of an electrogenerated silyl cation with H2O.
Highly Efficient Iridium-Catalyzed Oxidation of Organosilanes to Silanols
Lee, Youngjun,Seomoon, Dong,Kim, Sundae,Han, Hoon,Chang, Sukbok,Lee, Phil Ho
, p. 1741 - 1743 (2007/10/03)
Hydrolytic oxidation of organosilanes to the corresponding silanols can be performed highly efficiently with a catalyst system of [IrCl(C8H 12)]2 under essentially neutral and mild conditions, and various types of silanols are produced in good to excellent yields.
Silicon-Nitrogen Bonds. XXXIX. Kinetic Studies on the Spontaneous Hydrolysis, Alcoholysis, and Phenolysis of Silylamines
Kaufmann, K.-D.,Gisbier, D.,Grosse-Ruyken, H.,Ruehlmann, K.
, p. 721 - 728 (2007/10/02)
It could be shown by polarimetric and DC-metric methods that hydrolysis, alcoholysis, and phenolysis of silylamines are of second order and lead to equilibria.The rate of equilibrium establishment is determined by the position of a preceding protonation equilibrium and by steric effects.The position of the equilibria depends on inductive and steric effects.The enthalpy of activation for the ethanolysis of Me3SiNHPh was determined to 27,2 kJ/mol and the entropy of activation to -231 J/K*mol.The mechanism of the reactions is given.
