72666-87-6Relevant articles and documents
Breaking C-O Bonds with Uranium: Uranyl Complexes as Selective Catalysts in the Hydrosilylation of Aldehydes
Monsigny, Louis,Thuéry, Pierre,Berthet, Jean-Claude,Cantat, Thibault
, p. 9025 - 9033 (2019/10/02)
We report herein the possibility to perform the hydrosilylation of carbonyls using actinide complexes as catalysts. While complexes of the uranyl ion [UO2]2+ have been poorly considered in catalysis, we show the potentialities of the Lewis acid [UO2(OTf)2] (1) in the catalytic hydrosilylation of a series of aldehydes. [UO2(OTf)2] proved to be a very active catalyst affording distinct reduction products depending on the nature of the reductant. With Et3SiH, a number of aliphatic and aromatic aldehydes are reduced into symmetric ethers, while iPr3SiH yielded silylated alcohols. Studies of the reaction mechanism led to the isolation of aldehyde/uranyl complexes, [UO2(OTf)2(4-Me2N-PhCHO)3], [UO2(μ-κ2-OTf)2(PhCHO)]n, and [UO2(μ-κ2-OTf)(κ1-OTf)(PhCHO)2]2, which have been fully characterized by NMR, IR, and single-crystal X-ray diffraction.
Indium-catalyzed reductive esterification of a carboxylic acid: Sequential preparation of an ester and symmetrical ether
Sakai, Norio,Usui, Yuta,Ikeda, Reiko,Konakahara, Takeo
supporting information; experimental part, p. 3397 - 3401 (2012/02/02)
An unprecedented reductive dimerization of two carboxylic acids to produce ester derivatives by a combination catalyst involving InBr3 and sulfuric acid is described. A sequential conversion of the in-situ formed ester to a symmetrical ether by indium-catalyzed deoxygenation of the ester with a hydrosilane in the same pot was also demonstrated. Copyright
Aminodifluorosulfinium salts: Selective fluorination reagents with enhanced thermal stability and ease of handling
Lheureux, Alexandre,Beaulieu, Francis,Bennett, Christopher,Bill, David R.,Clayton, Simon,Laflamme, Franois,Mirmehrabi, Mahmoud,Tadayon, Sam,Tovell, David,Couturier, Michel
experimental part, p. 3401 - 3411 (2010/07/07)
Diethylaminodifluorosulfinium tetrafluoroborate (XtalFluor-E) and morpholinodifluorosulfinium tetrafluoroborate (XtalFluor-M) are crystalline fluorinating agents that are more easily handled and significantly more stable than Deoxo-Fluor, DAST, and their analogues. These reagents can be prepared in a safer and more cost-efficient manner by avoiding the laborious and hazardous distillation of dialkylaminosulfur trifluorides. Unlike DAST, Deoxo-Fluor, and Fluolead, XtalFluor reagents do not generate highly corrosive free-HF and therefore can be used in standard borosilicate vessels. When used in conjunction with promoters such as Et3N3HF, Et3N2HF, or DBU, XtalFluor reagents effectively convert alcohols to alkyl fluorides and carbonyls to gem-difluorides. These reagents are typically more selective than DAST and Deoxo-Fluor and exhibit superior performance by providing significantly less elimination side products.
