- A convenient modification of the Gassman oxindole synthesis
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A modification of the Gassman oxindole synthesis is described that proceeds from anilines and ethyl (methylsulfinyl)acetate, using oxalyl chloride to activate the sulfoxide to facilitate the formation of the key N-S bonded intermediate. This procedure is particularly convenient for reactions carried out on smaller scales and for anilines that are susceptible to electrophilic halogenation.
- Wright, Stephen W.,McClure, Lester D.,Hageman, David L.
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- Rhodium(II)-catalyzed direct sulfenylation of diazooxindoles with disulfides
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Rhodium(ii)-catalyzed direct sulfenylation of diazooxindoles using disulfides as the sulfenylating agent was developed via intermolecular C-S bond formation. This novel protocol provides a rapid synthetic route to 3-alkylthiooxindoles, 3,3-dialkylthiooxindoles, or 3,3-diarylthiooxindoles in moderate to good yield. The transformation is proposed to proceed through sulfur ylide formation followed by S-S bond cleavage and rearrangement.
- Khanal, Hari Datta,Kim, Sung Hong,Lee, Yong Rok
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p. 58501 - 58510
(2016/07/07)
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- N-Chlorophthalimide as a mild and efficient chlorination reagent in the Gassman ortho alkylation of aromatic amines. Synthesis of 3-(methylthio)oxindoles
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A practical modification of the Gassman 3-(methylthio)oxindole synthesis is reported. In our method, substituted anilines and 2-(methylthio)acetamide were reacted under mild reaction conditions, in the presence of N-chlorophthalimide as a chlorinating agent to give α-amidosulfides, which, in the next step of the process, were cyclized to give 3-(methylthio)oxindoles. The method was successfully applied for the synthesis of the key intermediate, 2-(2-amino-3-benzoylphenyl)-2-(methylthio)acetamide, in the process of the preparation of nepafenac, a commonly used ophthalmic drug.
- Cybulski, Marcin,Formela, Adam,Fokt, Izabela
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p. 5423 - 5425
(2014/12/11)
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- A facile approach for the asymmetric synthesis of oxindoles with a 3-sulfenyl-substituted quaternary stereocenter
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With the employment of a threonine-incorporating multifunctional catalyst 9, Michael addition of 3-sulfenyloxindoles to nitroolefins proceeded stereoselectively, leading to the formation of oxindoles with a 3-sulfenyl-substituted quaternary center in excellent yields, and with high diastereoselectivities and excellent enantioselectivities.
- Dou, Xiaowei,Zhou, Bo,Yao, Weijun,Zhong, Fangrui,Jiang, Chunhui,Lu, Yixin
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supporting information
p. 4920 - 4923
(2013/10/22)
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- Synthesis of α-oxo-sulfines in the indole series
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(Chemical Equation Presented) Oxindole was found to react readily with thionyl chloride to give (in an excellent yield) the isolable sulfine (13a), which on heating (refluxing acetonitrile) gave isoindigo (15a). The dark violet 3-sulfinatooxindole (13a) readily reacted with 2,3-dimethylbutadiene to give a colorless cyclo-adduct (14a). The sulfine also reacted readily with various nucleophilic reagents, thus, thioloacetic acid gave 3-carboxymethylthiolo- oxindole (23a).
- Bergman, Jan,Romero, Ivan
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experimental part
p. 1215 - 1220
(2010/11/16)
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- Asymmetric synthesis of pyrrolidinoindolines. Application for the practical total synthesis of (-)-phenserine
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A versatile route to enantiopure 3,3-disubstituted oxindoles and 3a-substituted pyrrolidinoindolines is described in which diastereoselective dialkylation of enantiopure ditriflate 10 with oxindole enolates is the central step. These reactions are rare examples of alkylations of prostereogenic enolates with chiral sp3 electrophiles that proceed with high facial selectivity (10-20:1). The scope of this method is explored, and a model to rationalize the sense of stereoselection is advanced. This dialkylation chemistry was used to synthesize (-)-phenserine on a multigram scale in six steps and 43% overall yield from 5-methoxy-1,3-dimethyloxindole (27) and to complete a short formal total synthesis of (-)-physostigmine (2).
- Huang, Audris,Kodanko, Jeremy J.,Overman, Larry E.
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p. 14043 - 14053
(2007/10/03)
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- Oxindole derivatives
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The present invention is related to oxindole derivatives, compositions containing the same, and methods of use and manufacture of the same. Such compounds generally are useful pharmacologically as agents in those disease states alleviated by the alteration of mitogen activated signaling pathways in general, and in particular in the inhibition or antagonism of protein kinases, which pathologically involve aberrant cellular proliferation. Such disease states include tumor growth, restenosis, atherosclerosis, pain and thrombosis. In particular, the present invention relates to a series of substituted oxindole compounds, which exhibit Trk family protein tyrosine kinase inhibition, and which are useful in cancer therapy and chronic pain indications.
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- A VERSATILE AND EFFICIENT PROCESS TO 3-SUBSTITUTED INDOLES FROM ANILINES
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Borane-mediated reductive elimination of α-thiomethyl-, α-hydroxy-, or α-alkoxy-, α'-substituted oxindoles affords 3-substituted indoles in high yield.Isatins, available via several routes from oxindoles, also afford indoles.
- Wierenga, Wendell,Griffin, John,Warpehoski, Martha A.
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p. 2437 - 2440
(2007/10/02)
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- Synthesis of oxindoles from anilines and β-thio carboxylic esters or amides
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Preparing oxindoles and intermediates therefor by reacting an N-haloaniline with β-thio esters or β-thio amides to form an azasulfonium halide, reacting the azasulfonium halide with a base to form an ortho-[thio-ether (hydrocarbonoxycarbonyl) alkyl]aniline, or a [thio-ether (aminocarbonyl) alkyl]aniline, reacting the orthosubstituted aniline with an acid to form a 3-thio-ether-2-oxindole, and then reducing the 3-thio-ether-2-oxindole with Raney Nickel to form the 2-oxindole.
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- Process for preparing azasulfonium halide salts
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Preparing azasulfonium halide salt derivatives of an aniline by reacting a halogen with a non-carbonylic dihydrocarbon sulfide, a beta-carbonylic hydrocarbon sulfide, or a β-thio ester or amide to form a halogen: sulfur compound complex and then reacting the complex with an aniline to form the azasulfonium halide salts. The azasulfonium halide salts are useful as intermediates in processes for making ortho-alkylated anilines, indoles, and 2-oxindoles which have a variety of known uses.
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