14178-15-5Relevant articles and documents
Method for preparing diarylether compound based on CO2 participated C-F bond activation
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Paragraph 0012-0015, (2021/01/04)
The invention discloses a method for preparing a diarylether compound based on CO2 participated C-F bond activation, which comprises the following steps: adding an acetonitrile solution of a 2-fluoropyridine compound into a reaction container, sequentially adding a catalyst palladium acetate Pd(OAc)2, alkali cesium carbonate and phenylsilane PhSiH3, and replacing with CO2 gas for three times, andreacting for 24 hours under the conditions that the CO2 pressure is 1atm and the temperature is 25 DEG C, adding an ice-water mixture after the reaction is finished, performing extraction reaction, dichloromethane extraction, organic phase merging and drying, reduced pressure distillation and silica gel column chromatography to obtain a target product, namely the white solid diarylether compound.Compared with the prior art, the method has the advantages of mild reaction temperature, good selectivity, high yield, easiness in industrialization and the like.
Etherification of functionalized phenols with chloroheteroarenes at low palladium loading: Theoretical assessment of the role of triphosphane ligands in C-O reductive elimination
Platon, Melanie,Cui, Luchao,Mom, Sophal,Richard, Philippe,Saeys, Mark,Hierso, Jean-Cyrille
supporting information; experimental part, p. 3403 - 3414 (2012/02/02)
The present study highlights the potential of robust tridentate ferrocenylphosphanes with controlled conformation as catalytic auxiliaries in C-O bond formation reactions. Air-stable palladium triphosphane systems are efficient for selective heteroaryl ether synthesis by using as little as 0.2 mol% of catalyst. These findings represent an economically attractive and clean etherification of functionalized phenols, electron-rich, electron-poor and para-, meta- or ortho-substituted substrates, with heteroaryl chlorides, including pyridines, hydroxylated pyridine, pyrimidines and thiazole. The etherification tolerates very important functions in various positions, such as cyano, methoxy, amino, and fluoro groups, which is useful to synthesize bioactive molecules. DFT studies furthermore demonstrate that triphosphane ligands open up various new pathways for the C-O reductive elimination involving the third phosphane group. In particular, the rate for one of these new pathways is calculated to be about 1000 times faster than for reductive elimination from a complex with a similar ferrocenyl ligand, but without a phosphane group on the bottom Cp-ring. Coordination of the third phosphane group to the palladium(II) center is calculated to stabilize the transition state in this new pathway, thereby enhancing the reductive elimination rate. Copyright
