10278-46-3Relevant articles and documents
Amide Synthesis from Thiocarboxylic Acids and Amines by Spontaneous Reaction and Electrosynthesis
Tang, Li,Matuska, Jack H.,Huang, Yu-Han,He, Yan-Hong,Guan, Zhi
, p. 2570 - 2575 (2019)
Amide bond formation is one of the most important basic reactions in chemistry. A catalyst-free approach for constructing amide bonds from thiocarboxylic acids and amines was developed. The mechanistic studies showed that the disulfide was the key intermediate for this amide synthesis. Thiobenzoic acids could be automatically oxidized to disulfides in air, thioaliphatic acids could be electro-oxidized to disulfides, and the resulting disulfides reacted with amines to give the corresponding amides. By this method, various amides could be easily synthesized in excellent yields without using any catalyst or activator. The successful synthesis of bioactive compounds also highlights the synthetic utility of this strategy in medicinal chemistry.
Exploration of Cu-catalyzed regioselective hydrodehalogenation of o-haloanilides using EtOH as hydrogen source
Li, Min-Xin,Li, Mei-Ling,Tang, Yan-Ling,Sun, Yun,Qu, Lu,Huang, Feng,Mao, Ze-Wei
, (2021)
In present work, we have explored a Cu(acac)2/vasicine-catalyzed regioselective hydrodehalogenation methodology of o-haloanilides using EtOH as hydrogen source and solvent. The catalytic system could selectively dehalogenate 2-Br and 2-I, and features regioselective, efficient and functional group tolerance.
Facile conversion of thioamides into the corresponding amides in the presence of tetrabutylammonium bromide
Inamoto, Kiyofumi,Shiraishi, Mitsugu,Hiroya, Kou,Doi, Takayuki
, p. 3087 - 3090 (2010)
Desulfurization of thioamides was accomplished using a semicatalytic amount of Bu4NBr. The corresponding amides were obtained in high yields, with good functional group compatibility. Georg Thieme Verlag Stuttgart - New York.
Detection of weak hydrogen bonding to fluoro and nitro groups in solution using H/D exchange
Shugrue,Defrancisco,Metrano,Brink,Nomoto,Linton
, p. 2223 - 2227 (2016)
Hydrogen/deuterium (H/D) exchange can be a sensitive technique for measuring the strength of hydrogen bonding to neutral organic nitro and fluoro groups. The slower rates of reaction in comparison to suitable controls suggest that hydrogen bonding is present, albeit rather weak.
Examining the Impact of Heteroaryl Variants of PAd-DalPhos on Nickel-Catalyzed C(sp2)-N Cross-Couplings
Clark, Jillian S. K.,McGuire, Ryan T.,Lavoie, Christopher M.,Ferguson, Michael J.,Stradiotto, Mark
, p. 167 - 175 (2019)
We report herein on the synthesis of new heteroaryl analogues of PAd-DalPhos and related bis(di(o-tolyl)phosphino) ancillary ligand variants based on pyridine or thiophene backbone structures, and their application in nickel-catalyzed C(sp2)-N cross-couplings under challenging reaction conditions. The 3,4-disubstituted thiophene-based ancillary ligand ThioPAd-DalPhos (L8) was observed to be particularly effective in the nickel-catalyzed C(sp2)-N cross-coupling of primary alkylamines, and the derived precatalyst (L8)NiCl(o-tolyl) (C2) was found to offer improved performance versus the related PAd-DalPhos-derived precatalyst C1 in such transformations. In using C2, cross-couplings of various primary alkylamines and (hetero)aryl-X electrophiles (X = Cl, Br, OTs) proceeded under unprecedentedly mild reaction conditions (0.25-0.50 mol % Ni), including examples conducted at room temperature. Also reported herein are the results of our combined experimental/DFT computational study directed toward gaining insight regarding the improved catalytic performance of C2 versus C1.
Molybdenum-mediated desulfurization of dhiols and disulfides
Wang, Zhen,Kuninobu, Yoichiro,Kanai, Motomu
, p. 1869 - 1872 (2014)
We have successfully achieved the molybdenum hexacarbonyl [Mo(CO) 6] mediated desulfurization of thiols and disulfides. In this reaction, the sulfhydryl (SH) mercapto groups of aryl, benzyl, primary and secondary alkyl thiols, and S-S single bonds of disulfides can be removed. This reaction has high functional group tolerance and is not affected by steric hindrance. The results of the reactions in acetone-d 6 suggest that the sources of hydrogen in the thiol and disulfide desulfurizations are the hydrogen atom(s) of a sulfhydryl group and acetone (solvent), respectively, and that the desulfurization proceeds via the formation of an organomolybdenum species. Georg Thieme Verlag Stuttgart. New York.
Nickel-Catalyzed N-Arylation of Primary Amides and Lactams with Activated (Hetero)aryl Electrophiles
Lavoie, Christopher M.,MacQueen, Preston M.,Stradiotto, Mark
, p. 18752 - 18755 (2016)
The first nickel-catalyzed N-arylation of amides with (hetero)aryl (pseudo)halides is reported, enabled by use of the air-stable pre-catalyst (PAd-DalPhos)Ni(o-tolyl)Cl (C1). A range of structurally diverse primary amides and lactams were cross-coupled successfully with activated (hetero)aryl chloride, bromide, triflate, tosylate, mesylate, and sulfamate electrophiles.
Amide bond formation from selenocarboxylates and aromatic azides
Wu, Xinghua,Hu, Longqin
, p. 8401 - 8405 (2005)
A new method of amide bond formation was developed through the reaction of potassium selenocarboxylates with aromatic azides at room temperature. Potassium selenocarboxylates were prepared in situ by the treatment of diacyl selenides with potassium methoxide at 5°C under N2. After the addition of azide, the reaction was allowed to gradually warm to room temperature and was stirred for 0.5-2 h. Excellent yields were obtained when electron deficient aromatic azides were used.
Bisphosphine-Ligated Nickel Pre-catalysts in C(sp2)–N Cross-Couplings of Aryl Chlorides: A Comparison of Nickel(I) and Nickel(II)
Lavoie, Christopher M.,McDonald, Robert,Johnson, Erin R.,Stradiotto, Mark
, p. 2972 - 2980 (2017)
The influence of ancillary ligand and nickel oxidation state in the nickel-catalyzed C(sp2)–N cross-coupling of aryl chlorides is examined by use of experimental and DFT methods for the first time, focusing on (L)NiCl and (L)Ni(o-tolyl)Cl pre-catalysts (PAd-DalPhos, L1; dppf, L2). Whereas Ni(II) pre-catalysts generally out-performed Ni(I) species in our study, the viability and in some cases superiority of Ni(I) pre-catalysts in challenging aminations is established. Computational analyses support the viability of Ni(0)/Ni(II) cycles featuring rate-limiting C–N reductive elimination, as well as parallel Ni(I)/Ni(III) mechanisms involving rate-limiting C–Cl oxidative addition. (Figure presented.).
An unsymmetrical covalent organic polymer for catalytic amide synthesis
Yadav, Deepika,Awasthi, Satish Kumar
, p. 179 - 186 (2019)
Herein, we present the first report on the Covalent Organic Polymer (COP) directed non-classical synthesis of an amide bond. An economical route has been chosen for the synthesis of APC-COP using p-aminophenol and cyanuric chloride. APC-COP acts as a smart, valuable and sustainable catalyst for efficient access to the amide bond under mild conditions at room temperature in 30 min. APC-COP exhibits selectivity towards carboxylic acids over esters. The key features of this protocol involve the variety of parameters, viz. wider substrate scope, no use of additive and recyclability, which makes this approach highly desirable in gramscale synthesis. Moreover, we have shown the practical utility of the present method in the catalytic synthesis of paracetamol.
