1859-70-7Relevant articles and documents
An advantageous route to oxcarbazepine (Trileptal) based on palladium-catalyzed arylations free of transmetallating agents
Carril, Monica,SanMartin, Raul,Churruca, Fatima,Tellitu, Imanol,Dominguez, Esther
, p. 4787 - 4789 (2005)
(Chemical Equation Presented) A new route to oxcarbazepine (Trileptal), the most widely prescribed antiepileptic drug, starting from commercially available 2′-aminoacetophenone and 1,2-dibromobenzene, is reported. The sequentially accomplished key steps are palladium-catalyzed intermolecular α-arylation of ketone enolates and intramolecular N-arylation reactions. After several experiments to establish the best conditions for both arylation processes, the target oxcarbazepine is obtained in a satisfactory overall yield, minimizing the number of steps and employing scalable catalytic procedures developed in partially aqueous media.
One-pot synthesis of 2,3-disubstituted N-tosylindoles from o-acyl-N-tosylanilines
Hari, Yoshiyuki,Kanie, Tomoki,Miyagi, Takashi,Aoyama, Toyohiko
, p. 1249 - 1252 (2006)
The reaction of oacyl-N-tosylanilines with lithium trimethylsilyldiazomethane followed by treatment with t-BuLi and then electrophiles gave 2,3-disubstituted N-tosylindoles in a one-pot process. Georg Thieme Verlag Stuttgart.
Iron-Catalyzed Electrophilic Amination of Sodium Sulfinates with Anthranils
Liang, Baihui,Huang, Junjie,Zhu, Weidong,Li, Yawen,Jiang, Lanping,Gao, Yang,Xie, Feng,Li, Yibiao,Chen, Xiuwen,Zhu, Zhongzhi
, p. 1466 - 1473 (2021/02/09)
A practical method for the synthesis of N-(2-carbonylaryl) benzenesulfonamides via an iron-catalyzed electrophilic amination of sodium sulfinates with anthranils is described. This redox-neutral transformation has high atom efficiency and is achieved under simple and mild reaction conditions. A wide range of anthranils and sodium sulfinates were compatible in this transformation. Moreover, the synthetic potential of this methodology was further demonstrated by the synthesis of various useful N-heterocycles and derivatives.
C-to N-Center Remote Heteroaryl Migration via Electrochemical Initiation of N Radical by Organic Catalyst
Liu, Chengkou,Jiang, Qiang,Lin, Yang,Fang, Zheng,Guo, Kai
supporting information, p. 795 - 799 (2020/02/04)
Herein an exogenous oxidant- A nd metal-free electrochemical heteroaryl migration triggered by N radicals to construct new N-C bonds was developed. This methodology features a high atom economy and utilization rate of energy, and it is insensitive to water and air. Moreover, a user-friendly undivided cell was employed. The use of an organic catalyst makes it more efficient, green, and practical.
Visible-light-promoted N-centered radical generation for remote heteroaryl migration
Cai, Chen,Fang, Zheng,Guo, Kai,Jiang, Qiang,Liu, Chengkou,Yuan, Chengcheng
supporting information, p. 7663 - 7670 (2020/10/14)
Herein, an efficient visible-light-mediated N-H heteroarylationviaremote heteroarylipso-migration has been accomplished. Moderate to good yields were obtained with good functional group tolerance. Moreover, a simple and readily available organic photoredox catalyst was employed, avoiding the use of complex and costly noble metal compounds.
Synthesis method of o-acylaniline sulfonamide compound
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Paragraph 0145-0151, (2020/10/30)
The invention discloses a synthesis method of a o-acylaniline sulfonamide compound. The preparation method is characterized by comprising the following steps: mixing a benzisoxazole compound as shownin a chemical formula I, a sodium sulfinate compound as shown in a chemical formula II, a metal catalyst and a solvent, and reacting to obtain the o-acylaniline sulfonamide compound as shown in a chemical formula III, in the formula, R1 is a monosubstituted or polysubstituted group on a benzene ring. The synthesis method can be used for efficiently synthesizing the o-acylaniline sulfonamide compound, has the advantages of simple synthesis steps, safety in operation, good compatibility of the synthesis method to functional groups and high atom economy, and is easy for industrial synthesis.
Manganese-Catalyzed ortho-C-H Amidation of Weakly Coordinating Aromatic Ketones
Kong, Xianqiang,Xu, Bo
, p. 4495 - 4498 (2018/08/07)
An efficient manganese-catalyzed ortho-C-H amidation of weakly coordinating aromatic ketones using the readily available sulfonyl azide as the amination reagent is developed. The key step is the ketone directed aromatic metalation using the in situ generated reactive Mn intermediate, MnMe(CO)5. This method offers excellent chemical yields, high regioselectivities, and good functional group tolerance.
Triple Mode of Alkylation with Ethyl Bromodifluoroacetate: N, or O-Difluoromethylation, N-Ethylation and S-(ethoxycarbonyl)difluoromethylation
Polley, Arghya,Bairy, Gurupada,Das, Pritha,Jana, Ranjan
supporting information, p. 4161 - 4167 (2018/09/21)
In this report, we have explored a triple mode of chemical reactivity of ethyl bromodifluoroacetate. Typically, bromodifluoroacetic acid has been used as a difluorocarbene precursor for difluoromethylation of soft nucleophiles. Here we have disclosed nucleophilicity and base dependent divergent chemical reactivity of ethyl bromodifluoroacetate. It furnishes lithium hydroxide and cesium carbonate promoted difluoromethylation of tosyl-protected aniline and electron-deficient phenols respectively. Interestingly, switching the base from lithium hydroxide to 4-N,N-dimethylamino pyridine (DMAP) tosyl-protected anilines afforded the corresponding N-ethylation product. Whereas, highly nucleophilic thiophenols furnished the corresponding S-carboethoxydifluoromethylation product via a rapid SN2 attack to the bromine atom prior to the ester hydrolysis. This mechanistic divergence was established through several control experiments. It was revealed that difluoromethylation reaction proceeds through a tandem in situ ester hydrolysis/decarboxylative-debrominative difluorocarbene formation and subsequent trapping by the soft nucleophile-NHTs or electron-deficient phenolic ?OH groups. In the presence of DMAP the hydrolysis of the ester is perturbed instead a nucleophilic attack at the ethyl moiety provides the N-ethylation product. Hence, besides the development of a practical base-promoted N-difluoromethylation of amines and electron-deficient phenols, divergent reactivity pattern of inexpensive and user-friendly ethyl bromodifluoroacetate has been explored. (Figure presented.).
Domino Aryne Annulation via a Nucleophilic-Ene Process
Xu, Hai,He, Jia,Shi, Jiarong,Tan, Liang,Qiu, Dachuan,Luo, Xiaohua,Li, Yang
supporting information, p. 3555 - 3559 (2018/03/21)
1,2-Benzdiyne equivalents possess the unique property that they can react with two arynophiles through iteratively generated 1,2- and 2,3-aryne intermediates. Upon rational modification on the second leaving group of these aryne precursors, a domino aryne annulation approach was developed through a nucleophilic-ene reaction sequence. Various benzo-fused N-heterocyclic frameworks were achievable under transition metal-free conditions with a broad substrate scope.
Nickel-Catalyzed Synthesis of Benzo[ b]naphtho[1,2- d]azepine via Intramolecular Radical Tandem Cyclization of Alkyl Bromide-Tethered Alkylidenecyclopropanes
Jiang, Bo,Liu, Jia-Xin,Wei, Yin,Shi, Min
supporting information, p. 6229 - 6233 (2018/10/05)
A Ni(II)-catalyzed tandem cyclopropane ring opening and radical alkylation of the aromatic ring using unactivated alkyl bromide-tethered alkylidenecyclopropanes (ACPs) have been described in this paper. This ring-forming process exhibits a broad substrate scope with a variety of primary alkyl bromides and aromatic rings, affording diversified benzo[b]naphtho[1,2-d]azepine derivatives in moderate-to-excellent yields under mild conditions. Plausible reaction mechanisms have been proposed on the basis of several control experiments, including the deuterium labeling examinations. Further derivatization of the obtained polycyclic product has also been performed.
