88584-52-5Relevant 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.
Copper(II) triflate-catalyzed reduction of carboxylic acids to alcohols and reductive etherification of carbonyl compounds
Zhang, Yin-Jie,Dayoub, Wissam,Chen, Guo-Rong,Lemaire, Marc
experimental part, p. 7400 - 7407 (2012/09/10)
A protocol is described for the reduction of carboxylic acids to primary alcohols using 1,1,3,3-tetramethyldisiloxane (TMDS) and a catalytic amount of Cu(OTf)2. Aliphatic as well as aromatic carboxylic acids are reduced in high selectivity and good yields. TMDS/Cu(OTf)2 has also been found to be an efficient catalytic reducing system for the preparation of symmetrical ethers from carbonyl compounds under mild conditions.
Reactivities of Carbonyl Compounds in Acid-Catalyzed Hydride Transfer vs. Electron Transfer
Fukuzumi, Shunichi,Fujita, Morifumi
, p. 2059 - 2062 (2007/10/02)
Rate constants for acid-catalyzed hydride-transfer reactions from triethylsilane to a series of carbonyl compounds are compared with those for acid-catalyzed electron transfer from the excited state of 2+ to the same series of carbonyl compounds in the presence of HClO4 in acetonitrile at 298 K.
