332-14-9Relevant articles and documents
B(C6F5)3-catalyzed tandem protonation/deuteration and reduction of: In situ -formed enamines
Wu, Rongpei,Gao, Ke
supporting information, p. 4032 - 4036 (2021/05/19)
A highly efficient B(C6F5)3-catalyzed tandem protonation/deuteration and reduction of in situ-formed enamines in the presence of water and pinacolborane was developed. Regioselective β-deuteration of tertiary amines was achieved with high chemo- and regioselectivity. D2O was used as a readily available and cheap source of deuterium. Mechanistic studies indicated that B(C6F5)3 could activate water to promote the protonation and reduction of enamines. This journal is
Method for catalyzing hydrodesulfurization of thioamide derivative
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Paragraph 0044-0048, (2021/07/09)
The invention provides a method for catalyzing hydrodesulfurization of a thioamide derivative, which comprises the following steps: sequentially adding a pentacarbonyl manganese bromide catalyst, a reaction substrate thioamide derivative, Lewis acid, a solvent and alkali into a polytetrafluoroethylene lined reaction tube, putting the reaction tube into a high-pressure kettle, introducing hydrogen to carry out catalytic hydrogenation reaction, cooling to room temperature, discharging gas, washing the reaction tube with ethyl acetate, passing through a silica gel small short column, carrying out spin drying, and carrying out column chromatography purification to obtain a target product. The monovalent manganese which is low in toxicity and good in chemical selectivity and biocompatibility is used as the catalyst to catalyze hydrodesulfurization of the thioamide derivative, the substrate range is wide, the yield of amine is high, and the method has high drug synthesis application value.
Alkali metal and stoichiometric effects in intermolecular hydroamination catalysed by lithium, sodium and potassium magnesiates
Davin, Laia,Hernán-Gómez, Alberto,McLaughlin, Calum,Kennedy, Alan R.,McLellan, Ross,Hevia, Eva
, p. 8122 - 8130 (2019/06/18)
Main group bimetallic complexes, while being increasingly used in stoichiometric deprotonation and metal-halogen exchange reactions, have not yet made a significant impact in catalytic applications. This paper explores the ability of alkali metal magnesiates to catalyse the intermolecular hydroamination of alkynes and alkenes using sytrene and diphenylacetylene as principle setting model substrates. By systematically studying the role of the alkali-metal and the formulation of the heterobimetallic precatalyst, this study establishes higher order potassium magnesiate [(PMDETA)2K2Mg(CH2SiMe3)4] (7) as a highly effective system capable of catalysing hydroamination of styrene and diphenylacetylene with several amines while operating at room temperature. This high reactivity contrasts with the complete lack of catalytic ability of neutral Mg(CH2SiMe3)2, even when harsher reaction conditions are employed (24 h, 80 °C). A pronounced alkali metal effect is also uncovered proving that the alkali metal (Li, Na, or K) is not a mere spectating counterion. Through stoichiometric reactions, and structural and spectroscopic (DOSY NMR) investigations we shed some light on the potential reaction pathway as well as the constitution of key intermediates. This work suggests that the enhanced catalytic activity of 7 can be rationalised in terms of the superior nucleophilic power of the formally dianionic magnesiate {Mg(NR2)4}2- generated in situ during the hydroamination process, along with the ability of potassium to engage in π-interactions with the unsaturated organic substrate, enhancing its susceptibility towards a nucleophilic attack by the amide anion.
