76412-58-3Relevant academic research and scientific papers
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.
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.
A very mild and selective method for O-benzoylation of hydroxamic acids
Zheng, Yongsheng,Liu, Muqiong,Yuan, Yu
supporting information, p. 4404 - 4406 (2014/07/22)
Selective O-benzoylation of hydroxamic acids is achieved by the treatment of BPO and DABCO. Aliphatic alcohols are not reactive under these conditions. Various radical or oxidation sensitive functional groups are compatible with this protocol, and no anhydrous reagents or solvents are required for the high yields of the benzoylations.
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
