584-02-1Relevant articles and documents
Kibby,Hall
, p. 65 (1973)
REACTION OF DIALKYLMAGNESIUM WITH CARBON MONOXIDE AND NITROSODURENE
Sobota, Piotr,Nowak, Marek,Kramarz, Wanda
, p. 161 - 168 (1984)
Reaction between diethylmagnesium and carbon monoxide gives rise to the formation of pentanone-3, pentanol-3, 3-ethylpentanol-3, 3-ethyl-3-hydroxyhexanone-4 and 3-ethylhexanone-4.The use of CO and application of C NMR spectroscopy revealed that C2H5COCH(C2H5)2 arose after hydrolysis of C2H5COC(C2H5)2MgC2H5.Reaction between (C2H5)2Mg and nitrosodurene proceeds according to the nitrene-radical mechanism and the EPR spectrum presents a signal derived from Me4PhN(radical)-N(PhMe4)OMgC2H5.Upon this basis a carbene-radical mechanism is proposed for the reaction between carbon monoxide and diethylmagnesium.
Manganese-Catalyzed Hydrogenation of Ketones under Mild and Base-free Conditions
Brünig, Julian,Kirchner, Karl,Veiros, Luis F.,Weber, Stefan
supporting information, p. 1388 - 1394 (2021/05/31)
In this paper, several Mn(I) complexes were applied as catalysts for the homogeneous hydrogenation of ketones. The most active precatalyst is the bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dippe) (CO)3(CH2CH2CH3)]. The reaction proceeds at room temperature under base-free conditions with a catalyst loading of 3 mol % and a hydrogen pressure of 10 bar. A temperature-dependent selectivity for the reduction of α,β-unsaturated carbonyls was observed. At room temperature, the carbonyl group was selectively hydrogenated, while the C=C bond stayed intact. At 60 °C, fully saturated systems were obtained. A plausible mechanism based on DFT calculations which involves an inner-sphere hydride transfer is proposed.
Ambient Hydrogenation and Deuteration of Alkenes Using a Nanostructured Ni-Core–Shell Catalyst
Beller, Matthias,Feng, Lu,Gao, Jie,Jackstell, Ralf,Jagadeesh, Rajenahally V.,Liu, Yuefeng,Ma, Rui
supporting information, p. 18591 - 18598 (2021/06/28)
A general protocol for the selective hydrogenation and deuteration of a variety of alkenes is presented. Key to success for these reactions is the use of a specific nickel-graphitic shell-based core–shell-structured catalyst, which is conveniently prepared by impregnation and subsequent calcination of nickel nitrate on carbon at 450 °C under argon. Applying this nanostructured catalyst, both terminal and internal alkenes, which are of industrial and commercial importance, were selectively hydrogenated and deuterated at ambient conditions (room temperature, using 1 bar hydrogen or 1 bar deuterium), giving access to the corresponding alkanes and deuterium-labeled alkanes in good to excellent yields. The synthetic utility and practicability of this Ni-based hydrogenation protocol is demonstrated by gram-scale reactions as well as efficient catalyst recycling experiments.
Chromium-Catalyzed Production of Diols From Olefins
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Paragraph 0111, (2021/03/19)
Processes for converting an olefin reactant into a diol compound are disclosed, and these processes include the steps of contacting the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and hydrolyzing the reduced chromium catalyst to form a reaction product comprising the diol compound. While being contacted, the olefin reactant and the supported chromium catalyst can be irradiated with a light beam at a wavelength in the UV-visible spectrum. Optionally, these processes can further comprise a step of calcining at least a portion of the reduced chromium catalyst to regenerate the supported chromium catalyst.
