2171-96-2Relevant articles and documents
Partial reduction of trimethoxyborane: An old reaction in a new reactor
Jeffers, Peter M.,Bauer
, p. 1698 - 1701 (1981)
Forty-fifty percent conversion of trimethoxyborane to HB(OCH3)2 was achieved by passing B(OCH3)3/H2 mixtures through a carefully controlled microwave discharge; almost all of the unconverted reactants were recovered. Similar but much less efficient reductions were obtained by exposing the reactants to focused pulses of CO2 laser radiation [P(26)-P(34) lines of the 9.6-μm band]. We were not successful in reducing trimethoxyborane by activating these mixtures with electrical discharges, with continuous, unfocused laser radiation, or via Hg-photosensitized photolysis. No significant reductions were achieved by any mode of excitation when H2S, NH3, C2H2, or CH4 replaced the H2. However, the reaction B(OCH3)3 + SiH4 = HB(OCH3)2 + SiH3(OCH3) proceeds smoothly under CW laser irradiation.
Catalytic CO2 hydrosilylation with [Mn(CO)5Br] under mild reaction conditions
García, Juventino J.,González, Tania
supporting information, (2021/06/07)
Carbon dioxide hydrosilylation with earth-abundant transition-metal catalysts is an attractive alternative for the design of greener and cost-effective synthetic strategies. Herein, simple [Mn(CO)5Br] is an efficient precatalyst in the hydrosilylation of carbon dioxide with Et3SiH under mild reaction conditions. Using THF as a solvent, triethylsilylformate Et3SiCH(O)O was obtained in 67% yield after 1 h at 50 °C and 4 bar of CO2 pressure. The selectivity of the reaction was tuned by changing the solvent to a mixture of THF and toluene producing bis(triethylsilyl)acetal (Et3SiO)2CH2 in 86% yield. The CO2 hydrosilylation was also effective at room temperature and atmospheric pressure using either THF or the mixture THF/toluene as the solvent resulting in high Et3SiH conversion (92%–99%) but with a decrease in the selectivity. Radical trapping experiments indicated the participation of radical species in the catalytic mechanism. To the best of our knowledge, this is the first report on CO2 hydrosilylation catalyzed by transition-metal radical intermediates.
Copper(II)-Catalyzed Selective Reductive Methylation of Amines with Formic Acid: An Option for Indirect Utilization of CO2
Qiao, Chang,Liu, Xiao-Fang,Liu, Xi,He, Liang-Nian
supporting information, p. 1490 - 1493 (2017/03/23)
A copper-catalyzed protocol for reductive methylation of amines and imine with formic acid as a C1 source and phenylsilane as a reductant is reported for the first time, affording the corresponding methylamines in good to excellent yields under mild conditions. This protocol offers an alternative method for indirect utilization of CO2, as formic acid can be readily obtained from hydrogenation of CO2.
