959-32-0Relevant articles and documents
N,O-diacylhydroxylamines - Structures in crystals and solutions
Schraml, Jan,Sykora, Jan,Fiedler, Pavel,Roithova, Jana,Mindl, Jaromir,Blechta, Vratislav,Cisarova, Ivana,Exner, Otto
, p. 2311 - 2314 (2004)
The structures of four N,O-diacylhydroxylamines (RCOHNOCOR′, R, R′ = Me, Ph) were determined in the solid state by X-ray diffraction and studied by NMR and IR spectroscopies in solution. The interpretation of the results was supported by ab-initio calcula
Synthesis of sulfimides and N-Allyl-N-(thio)amides by Ru(II)catalyzed nitrene transfer reactions of N-acyloxyamides
Zhang, Xinyu,Lin, Bo,Chen, Jianhui,Chen, Jiajia,Luo, Yanshu,Xia, Yuanzhi
supporting information, p. 819 - 825 (2021/02/01)
The N-acyloxyamides were employed as effective N-acyl nitrene precursors in reactions with thioethers under the catalysis of a commercially available Ru(II) complex, from which a variety of sulfimides were synthesized efficiently and mildly. If an allyl group is contained in the thioether precursor, the [2,3]-sigmatropic rearrangement of the sulfimide occurs simultaneously and the N-allyl-N-(thio)amides were obtained as the final products. Preliminary mechanistic studies indicated that the Ru-nitrenoid species should be a key intermediate in the transformation.
Facile synthesis ofO-acylhydroxamatesviareaction of oxime chlorides with carboxylic acids
Chen, Rongxiang,Li, Yan-Li,Sun, Aili,Wang, Kai-Kai,Zhang, Shan-Shan,Zhao, Ying-Chao
, p. 40193 - 40196 (2021/12/31)
A simple and efficient method for the synthesis ofO-acylhydroxamate derivatives from oxime chlorides and carboxylic acids was developed. The reaction affords clean and facile access to diverseO-acylhydroxamates in high yields (up to 85%). The chemical structure of a typical product was confirmed using single-crystal X-ray structure analysis.
NiH-Catalyzed Proximal-Selective Hydroamination of Unactivated Alkenes
Jeon, Jinwon,Lee, Changseok,Seo, Huiyeong,Hong, Sungwoo
supporting information, p. 20470 - 20480 (2020/11/27)
Reported herein is a modular, NiH-catalyzed system capable of proximal-selective hydroamination of unactivated alkenes with diverse amine sources. The key to the successful implementation of this approach is the promotion of NiH insertion into even highly substituted olefins via coordination of the bidentate directing group to the nickel complex. A wide range of primary and secondary amines can be installed in both internal and terminal unactivated alkenes with excellent regiocontrol under the optimized reaction conditions. This protocol is flexible and general for the preparation of a variety of valuable β- and γ-amino acid building blocks that would otherwise be difficult to synthesize. The utility of this transformation was further demonstrated by the site-selective late-stage modification of complex and medicinally relevant molecules. Combined experimental and computational studies illuminate the detailed reaction mechanism.
The Easy Approach to N -Hydroxy- N -cycloalkenylamides through Nitrosocarbonyl Ene Reactions to Cycloalkenes: Valuable Compounds for Antiviral Syntheses
Hameed, Karzan Khaleel,Amin, Ahmed Anwar,Hussain, Faiq H. S.,Memeo, Misal Giuseppe,Moiola, Mattia,Quadrelli, Paolo
, p. 1383 - 1390 (2019/03/08)
An easy approach to N -hydroxy- N -cycloalkenylamides, ene adducts of cyclic alkenes of different sizes, is presented. The products can be obtained both through the thermal generation of the nitrosocarbonyl intermediates and via the photochemical fragment
Direct Observation of Acyl Nitroso Compounds in Aqueous Solution and the Kinetics of Their Reactions with Amines, Thiols, and Hydroxamic Acids
Maimon, Eric,Lerner, Ana,Samuni, Amram,Goldstein, Sara
, p. 7006 - 7013 (2018/09/06)
Acyl nitroso compounds or nitrosocarhonyls (RC(O)N=O) are reactive short-lived electrophiles, and their hydrolysis and reactions with nucleophiles produce HNO. Previously, direct detection of acyl nitroso species in nonaqueous media has been provided by time-resolved infrared spectroscopy demonstrating that its half-life is about 1 ms. In the present study hydroxamic acids (RC(O)NHOH) are oxidized electrochemically in buffered aqueous solutions (pH 5.9-10.2) yielding transient species characterized by their maximal absorption at 314-330 nm. These transient species decompose via a first-order reaction yielding mainly HNO and the respective carboxylic acid and therefore are ascribed to RC(O)N=O. The sufficiently long half-life of RC(O)N=O in aqueous solution allows for the first time the study of the kinetics of its reactions with various nucleophiles demonstrating that the nucleophilic reactivity follows the order thiolate > hydroxamate > amine. Metal chelates of CH3C(O)NHOH catalyze the hydrolysis of CH3C(O)N=O at the efficacy order of CuII > ZnII > NiII > CoII where only CuII catalyzes the hydrolysis also in the absence of the hydroxamate. Finally, oxidation of hydroxamic acids generates HNO, and the rate of this process is determined by the half-life of the respective acyl nitroso compound.
Lossen rearrangements under heck reaction conditions
AbdelHafez, El-Shimaa M.N.,Aly, Omar M.,Abuo-Rahma, Gamal El-Din A.A.,King, S. Bruce
supporting information, p. 3456 - 3464 (2015/02/05)
The classical Lossen rearrangement converts activated hydroxamic acids to isocyanates that form numerous products upon their reaction with nucleophiles. We report a simple and highly efficient method of using Heck reaction conditions to initiate Lossen rearrangements of hydroxamic acids. In addition, Lossen rearrangements occur in the presence of palladium(II) acetate or triethylamine, components of the Heck reaction, alone. A potential mechanism is provided to explain this reactivity and these results show that Heck reactions and Lossen rearrangements occur under the same conditions and may provide new methods for facile initiation of Lossen rearrangements.
O-nucleophilicity of hydroxamate ions for cleavage of carboxylate and phosphate esters in cationic micelles
Satnami, Manmohan L.,Karbhal, Indrapal,Dewangan, Hitesh K.
supporting information, p. 419 - 432 (2014/07/08)
The nucleophilic reactivities of hydroxamate (HA-) ions of the structure RCONHO- [R = CH3 (acetohydroxamate, AHA -), C6H5 (benzohydroxamate, BHA-), 2-OHC6H4
Rhodium(III)-catalyzed heterocycle synthesis using an internal oxidant: Improved reactivity and mechanistic studies
Guimond, Nicolas,Gorelsky, Serge I.,Fagnou, Keith
supporting information; experimental part, p. 6449 - 6457 (2011/06/16)
Directing groups that can act as internal oxidants have recently been shown to be beneficial in metal-catalyzed heterocycle syntheses that undergo C-H functionalization. Pursuant to the rhodium(III)-catalyzed redox-neutral isoquinolone synthesis that we recently reported, we present in this article the development of a more reactive internal oxidant/directing group that can promote the formation of a wide variety of isoquinolones at room temperature while employing low catalyst loadings (0.5 mol %). In contrast to previously reported oxidative rhodium(III)-catalyzed heterocycle syntheses, the new conditions allow for the first time the use of terminal alkynes. Also, it is shown that the use of alkenes, including ethylene, instead of alkynes leads to the room temperature formation of 3,4-dihydroisoquinolones. Mechanistic investigations of this new system point to a change in the turnover limiting step of the catalytic cycle relative to the previously reported conditions. Concerted metalation-deprotonation (CMD) is now proposed to be the turnover limiting step. In addition, DFT calculations conducted on this system agree with a stepwise C-N bond reductive elimination/N-O bond oxidative addition mechanism to afford the desired heterocycle. Concepts highlighted by the calculations were found to be consistent with experimental results.
First O-glycosylation of hydroxamic acids
Thomas, Mickael,Gesson, Jean-Pierre,Papot, Sebastien
, p. 4262 - 4264 (2008/02/05)
(Chemical Equation Presented) The first O-glycosylation of hydroxamic acids is reported. This process involves the use of glycosyl N-phenyl trifluoroacetimidates as glycosyl donors in the presence TMSOTf and 4 A molecular sieves in dichloromethane. Under
