23132-29-8Relevant articles and documents
Hydration of Aliphatic Nitriles Catalyzed by an Osmium Polyhydride: Evidence for an Alternative Mechanism
Babón, Juan C.,Esteruelas, Miguel A.,López, Ana M.,O?ate, Enrique
, p. 7284 - 7296 (2021/05/29)
The hexahydride OsH6(PiPr3)2 competently catalyzes the hydration of aliphatic nitriles to amides. The main metal species under the catalytic conditions are the trihydride osmium(IV) amidate derivatives OsH3{κ2-N,O-[HNC(O)R]}(PiPr3)2, which have been isolated and fully characterized for R = iPr and tBu. The rate of hydration is proportional to the concentrations of the catalyst precursor, nitrile, and water. When these experimental findings and density functional theory calculations are combined, the mechanism of catalysis has been established. Complexes OsH3{κ2-N,O-[HNC(O)R]}(PiPr3)2 dissociate the carbonyl group of the chelate to afford κ1-N-amidate derivatives, which coordinate the nitrile. The subsequent attack of an external water molecule to both the C(sp) atom of the nitrile and the N atom of the amidate affords the amide and regenerates the κ1-N-amidate catalysts. The attack is concerted and takes place through a cyclic six-membered transition state, which involves Cnitrile···O-H···Namidate interactions. Before the attack, the free carbonyl group of the κ1-N-amidate ligand fixes the water molecule in the vicinity of the C(sp) atom of the nitrile.
Enantioselective Ruthenium(II)/Xyl-SunPhos/Daipen-Catalyzed hydrogenation of γ-Ketoamides
Zhao, Mengmeng,Li, Wanfang,Li, Xiaoming,Ren, Kai,Tao, Xiaoming,Xie, Xiaomin,Ayad, Tahar,Ratovelomanana-Vidal, Virginie,Zhang, Zhaowuo
, p. 6164 - 6171 (2014/07/21)
A0series of γ-hydroxy amides were synthesized with high ena~tioselectivities (up to 99%) usyng asymmetric hydrogenation of the corresponding γ-ketoamides in the presence of Ru-Xyl-SunPhos-Daipen catalyst providing key building blocks for a variety of natu
Elevation of HDL cholesterol by 4-[(Aminothioxomethyl)-hydrazono]-N-(substituted)-4-arylbutanamides
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, (2008/06/13)
Compounds of this invention increase plasma levels of high density lipoprotein or HDL, the “good” cholesterol and as such may be useful for treating diseases such as atherosclerosis. These compounds are represented by the formula wherein: R1, R2, and R3are independently hydrogen, C1-C6alkyl, phenyl or —(CH2)1-6phenyl where phenyl is optionally substituted by halogen, cyano, nitro, C1-C6alkyl, C1-C6alkoxy, trifluoromethyl, C1-C6alkoxycarbonyl, —CO2H or OH; R4and R5are independently hydrogen, C1-C10alkyl, C3-C8cycloalkyl, —(CH2)0-6Ar1where Ar1is phenyl, naphthyl, furanyl, pyridinyl or thenyl and Ar1can be optionally substituted by halogen, cyano, nitro, C1-C6alkyl, phenyl, C1-C6alkoxy, phenoxy, trifluoromethyl, C1-C6alkoxycarbonyl, —CO2H or OH, or R4and R5together with the nitrogen to which R4and R5are attached form a ring containing 4-7 carbon atoms; and Ar is phenyl, naphthyl, furanyl, pyridinyl or thienyl which may be optionally substituted by halogen, cyano, nitro, C1-C6alkyl, C3-C6cycloalkyl, phenyl, C1-C6alkoxy, phenoxy, trifluoromethyl, C1-C6alkoxycarbonyl, —CO2H or OH.
