53-63-4Relevant articles and documents
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Anner,Miescher
, p. 1379,1380,1383 (1950)
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Nickel-Catalyzed Intramolecular Decarbonylative Coupling of Aryl Selenol Esters
Bai, Jin-Hua,Qi, Xiu-Juan,Sun, Wei,Yu, Tian-Yang,Xu, Peng-Fei
supporting information, p. 2084 - 2088 (2021/03/01)
This report describes a method for Ni-catalyzed intramolecular decarbonylative coupling, which enables the conversion of areneselenol esters to diaryl selenides. The inexpensive and readily available catalyst can be employed under mild reaction conditions for the construction of structurally diverse diaryl selenides, including heterocyclic and natural product derivatives. (Figure presented.).
Selectivity and Mechanism of Iridium-Catalyzed Cyclohexyl Methyl Ether Cleavage
Fast, Caleb D.,Jones, Caleb A. H.,Schley, Nathan D.
, p. 6450 - 6456 (2020/07/13)
Cationic bis(phosphine)iridium complexes are found to catalyze the cleavage of cyclohexyl methyl ethers by triethylsilane. Selectivity for C-O cleavage is determined by the relative rates of SN2 demethylation versus SN1 demethoxylation, with the axial or equatorial disposition of the silyloxonium ion intermediate acting as an important contributing factor. Modulation of the electron-donor power of the supporting phosphine ligands enables a switch in selectivity from demethylation of equatorial methyl ethers to 2° demethoxylation. Applications of these accessible catalysts to the selective demethoxylation of the 3α-methoxy group of cholic acid derivatives is demonstrated, including a switch in observed selectivity controlled by 7α-substitution. The resting state of the catalyst has been characterized for two phosphine derivatives, demonstrating that the observed switch in C-O cleavage selectivity likely results from electronic factors rather than from a major perturbation of the catalyst structure.
Reducing dehalogenating method of organic halogenated compound
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Paragraph 0099; 0100; 0102; 0124; 0129; 0130, (2019/02/10)
The invention discloses a reducing dehalogenating method of an organic halogenated compound. The reducing dehalogenating method comprises: mixing an organic halogenated compound R-X, a non-noble metalpromoter, a sulfide and an alkali, and carrying out a reducing dehalogenating reaction to obtain a reducing product R-H, wherein R is at least one selected from alkyl and aryl, and X is at least oneselected from iodine, bromine and chlorine. According to the present invention, the types and the ratio (especially the specific type of the promoter) of various raw materials used in the reducing dehalogenating reaction, the corresponding reaction conditions and the like are researched and improved, such that the problems of use of highly-toxic or expensive reagent, poor tolerance of the group, narrow application range of the substrate and the like in the prior art can be effectively solved.
