- Electrochemical Umpolung C-H Functionalization of Oxindoles
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Herein, we present a general electrochemical method to access unsymmetrical 3,3-disubstituted oxindoles by direct C-H functionalization where the oxindole fragment behaves as an electrophile. This Umpolung approach does not rely on stoichiometric oxidants and proceeds under mild, environmentally benign conditions. Importantly, it enables the functionalization of these scaffolds through C-O, and by extension to C-C or even C-N bond formation.
- Pastor, Miryam,Vayer, Marie,Weinstabl, Harald,Maulide, Nuno
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supporting information
p. 606 - 612
(2022/01/12)
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- Rapid Oxidation Indoles into 2-Oxindoles Mediated by PIFA in Combination with n-Bu4NCl ? H2O
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We report the development of a rapid approach for directly converting indoles into 2-oxindoles promoted by HOCl formed in situ from the combination of (bis(trifluoroacetoxy) iodo)benzene (PIFA) and n-Bu4NCl ? H2O. The procedure is widely functional group tolerant and provides 2-oxindoles in up to 95% yield within 5 min. The potential applications of the developed methodology are demonstrated by the gram-scale preparation of 3-methyl-2-oxindole (11 a), the one-pot two-step syntheses of spiro-oxindoles 26 a and 26 b, and the formal synthesis of (-)-folicanthine (2). (Figure presented.).
- Liang, Peng,Zhao, Hang,Zhou, Tingting,Zeng, Kaiyun,Jiao, Wei,Pan, Yang,Liu, Yazhou,Fang, Dongmei,Ma, Xiaofeng,Shao, Huawu
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supporting information
p. 3532 - 3538
(2021/06/09)
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- Copper-Catalyzed Asymmetric Propargylic Alkylation with Oxindoles: Diastereo- A nd Enantioselective Construction of Vicinal Tertiary and All-Carbon Quaternary Stereocenters
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A copper-catalyzed asymmetric propargylic alkylation of propargylic acetates with 3-substituted oxindoles for the stereoselective construction of vicinal tertiary and all-carbon quaternary stereocenters in a 3,3-disubstituted oxindole skeleton has been realized. The reaction proceeded smoothly under the catalysis of Cu(MeCN)4PF6combined with a chiral tridentate ferrocenyl P,N,N ligand, leading to a broad range of optically active 3,3-disubstituted oxindoles in high yields and with excellent diastereo- A nd enantioselectivities.
- Xia, Jin-Tao,Hu, Xiang-Ping
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supporting information
p. 1102 - 1107
(2020/02/15)
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- Selective Insertion of Alkynes into C-C σ Bonds of Indolin-2-ones: Transition-Metal-Free Ring Expansion Reactions to Seven-Membered-Ring Benzolactams or Chromone Derivatives
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An unprecedented ring expansion reaction of indolin-2-ones with alkynyl ketones under transition-metal-free conditions has been developed. Base-promoted selective cleavage of a C-C σ bond of the amide is the key in this process, which provides a straightf
- Wang, Mengdan,Yang, Yajie,Song, Bo,Yin, Liqiang,Yan, Shuhui,Li, Yanzhong
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p. 155 - 159
(2020/01/03)
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- Palladium-Catalyzed Allylation of Cyclopropyl Acetylenes with Oxindoles to Construct 1,3-Dienes
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A novel palladium-catalyzed allylic alkylation of oxindoles with cyclopropyl acetylenes has been developed. Various 1,3-diene oxindole framework bearing a quaternary stereocenter at the C3 position were synthesized straightforwardly in good to excellent yields with high regio-, and stereoselectivities. The reaction exhibited high atom economy and good functional group tolerance.
- Lu, Chuan-Jun,Yu, Xin,Chen, Yu-Ting,Song, Qing-Bao,Yang, Zhen-Ping,Wang, Hong
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p. 680 - 688
(2020/02/11)
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- Synthesis of α-Aryl Oxindoles by Friedel-Crafts Alkylation of Arenes
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α-Aryl oxindoles are accessed from isatin via a two-step procedure involving a phospha-Brook rearrangement and a Friedel-Crafts alkylation in a one-pot procedure. The use of 1,1,1,3,3,3-hexafluoro-2-propanol as solvent significantly extended the reaction
- Guiry, Patrick J.,Rokade, Balaji V.
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p. 6172 - 6180
(2020/05/28)
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- Metal-free and regiospecific synthesis of 3-arylindoles
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A convenient, metal-free, and organic acid-base promoted synthetic method to prepare 3-arylindoles from 3-aryloxirane-2-carbonitriles and arylhydrazine hydrochlorides has been developed. In the reaction, the organic acid catalyzes a tandem nucleophilic ri
- Xie, Wenlai,Xu, Chuangchuang,Xu, Jiaxi
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p. 2661 - 2671
(2020/04/17)
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- A iron catalytic oxidation of indole synthesis of compounds 2 - indole ketone compounds (by machine translation)
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The invention discloses an iron catalytic oxidation indoles of synthesis of compounds 2 - indole ketone compounds, included in the organic solvent, water or an organic solvent in the aqueous solution, the hydrogen of the silane as promoter, in under the a
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Paragraph 0073-0075
(2019/10/04)
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- Organocatalytic stereoselective conjugate addition of 3-substituted oxindoles with in situ generated ortho-quinone methides
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A novel method for the stereoselective conjugate addition of 3-substituted oxindoles to in situ generated o-QMs was described. This process was catalyzed efficiently by a cinchonidine-derived squaramide catalyst in oil-water phase, furnishing the corresponding 3,3-disubsituted oxindole derivatives in moderate to high yields (up to 98%) with high stereoselectivities (up to 95% ee, 15.4:1 dr). The utility of this reaction was also investigated by the gram-scale synthesis and derivatization of one of the products.
- Liang, Weihong,Yin, Wenhao,Wang, Tingzhong,Qiu, Fayang G.,Zhao, Junling
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supporting information
p. 1742 - 1747
(2018/04/02)
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- Asymmetric organocatalytic α-amination of 2-oxindoles with bis(2,2,2-trichloroethyl)azo-dicarboxylate
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An enantioselective electrophilic amination of 3-substituted-2-oxindoles is reported, using bis(2,2,2-trichloroethyl)azo-dicarboxylate and commercially available Cinchona alkaloid organocatalysts. The best results were obtained in the reaction of 3-aryl s
- Bondanza, Mattia,Pescitelli, Gennaro,Mandoli, Alessandro
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supporting information
p. 2590 - 2594
(2018/05/29)
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- Preparation method of 3-substituted oxidized indole and derivative
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The invention belongs to the technical field of organic chemistry and pharmaceutical chemistry and particularly relates to a method of preparing 3-substituted oxidized indole and a derivative. In themethod, with a 3-substituted indole derivative as a raw material and one or more of a tetrabutyl ammonium halide compound/sodium chloride/sodium iodide/potassium iodide as additives, and one or more of dichloromethane/1,2-dichloroethane/tetrahydrofurane/methylbenzene/1,4-dioxane/ethyl acetate/methanol are added as solvents; then one or more of [bis(trifluoroacetoxyl)iodine]benzene/iodosobenzene diacetate are added as oxidants in order to carry out a reaction with reaction temperature being controlled, thus producing the 3-substituted oxidized indole derivative. The method has gentle reaction conditions, simple operations, short reaction time and high yield, and is free of a metal catalyst and is environment-friendly.
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- Ionic Liquid-Mediated Hydrofluorination of o-Azaxylylenes Derived from 3-Bromooxindoles
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The hydrofluorination reaction of 3-bromooxindole using mild HF reagents in an ionic liquid is described. This transformation can operate at room temperature to give a series of 3-substituted 3-fluorooxindole derivatives including racemic BMS 204352 (MaxiPost). The mechanistic study about interactions between HF and 3-butyl-1-methylimidazolium tetrafluoroborate [bmim][BF4] is also discussed on the basis of energy calculations.
- Mizuta, Satoshi,Otaki, Hiroki,Kitagawa, Ayako,Kitamura, Kanami,Morii, Yuki,Ishihara, Jun,Nishi, Kodai,Hashimoto, Ryo,Usui, Toshiya,Chiba, Kenya
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supporting information
p. 2572 - 2575
(2017/05/24)
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- Oxidative Fragmentations and Skeletal Rearrangements of Oxindole Derivatives
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An oxidative sequence for the conversion of oxindoles to structurally distinct heterocyclic scaffolds and aniline derivatives is disclosed by the combination of a copper-catalyzed C-H peroxidation and subsequent base-mediated fragmentation reaction. In contrast to classic enzymatic (i.e., kynurenine pathway) and biomimetic methods (i.e., Witkop-Winterfeldt oxidation) for oxidative indole cleavage, this protocol allows for the incorporation of external nucleophiles. The new transformation displays broad functional group tolerance and is applicable to tryptophan derivatives, opening potential new avenues for postsynthetic modification of polypeptides, bioconjugation, and unnatural amino acid synthesis.
- Klare, Hendrik F. T.,Goldberg, Alexander F. G.,Duquette, Douglas C.,Stoltz, Brian M.
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supporting information
p. 988 - 991
(2017/03/14)
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- Bifunctional tertiary amine-squaramide catalyzed asymmetric catalytic 1,6-conjugate addition/aromatization of para-quinone methides with oxindoles
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The asymmetric catalytic 1,6-addition of p-QMs with racemic oxindoles under the bifunctional catalysis of C2-symmetric dimeric Cinchona-derived squaramide is described. This tertiary amine-squaramide catalyzed reaction provides a diastereoselective and enantioselective approach to the effective assembly of diverse diarylmethine-substituted oxindoles having vicinal tertiary and quaternary stereocenters.
- Deng, Yu-Hua,Zhang, Xiang-Zhi,Yu, Ke-Yin,Yan, Xu,Du, Ji-Yuan,Huang, Hanmin,Fan, Chun-An
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supporting information
p. 4183 - 4186
(2016/03/19)
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- In situ generation of electrophilic trifluoromethylthio reagents for enantioselective trifluoromethylthiolation of oxindoles
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An organocatalytic asymmetric trifluoromethylthiolation reaction via in situ generation of active electrophilic trifluoromethylthio species involving trichloroisocyanuric acid and AgSCF3 as a practical and easily handled electrophilic SCF3 source for CSP 3-SCF3 bond formation was developed. Reactions with this one-pot version strategy occurred in good yields and excellent stereoselectivities to access enantiopure oxindoles bearing a SCF 3-substituted quaternary chiral center. The straightforward process described here makes use of simple starting materials and proceeds under mild conditions, which will be useful in medicinal chemistry and diversity-oriented syntheses.
- Zhu, Xing-Li,Xu, Jin-Hui,Cheng, Dao-Juan,Zhao, Li-Jiao,Liu, Xin-Yuan,Tan, Bin
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supporting information
p. 2192 - 2195
(2014/05/06)
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- Reduction of 3-aminoquinoline-2,4(1H,3H)-diones and deamination of the reaction products
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3-Aminoquinoline-2,4-diones were stereoselectively reduced with NaBH 4 to give cis-3-amino-3,4-dihydro-4-hydroxyquinolin-2(1H)-ones. Using triphosgene (=bis(trichloromethyl) carbonate), these compounds were converted to 3,3a-dihydrooxazolo[4,5-
- Klásek, Antonín,Ly?ka, Antonín,Rouchal, Michal,Rudolf, Ond?ej,R??i?ka, Ale?
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p. 595 - 612
(2014/06/09)
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- N-heterocyclic carbene-palladium(II)-1-methylimidazole complex catalyzed α-arylation of oxindoles with aryl chlorides and aerobic oxidation of the products in a one-pot procedure
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NHC-Pd(II)-Im complex 1 was found to be an effective catalyst for the α-arylation of unprotected oxindoles with aryl chlorides to give products 4 in 44-98% yields under a N2 atmosphere. Furthermore, if the reactions were first performed under conditions identical to those for the α-arylation reaction for 12 h and then exposed to air for another 3 h, 3-aryl-3-hydroxy-2-oxindoles 5 can be obtained in 49-84% yields in a one-pot procedure.
- Xiao, Zheng-Kang,Yin, Hui-Ying,Shao, Li-Xiong
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supporting information
p. 1254 - 1257
(2013/04/23)
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- Cinchona alkaloid catalyzed enantioselective chlorination of 3-aryloxindoles
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O-Benzoylquinidine is an effective organocatalyst for the asymmetric chlorination of 3-aryloxindoles by using easily available N-chlorosuccinimide (NCS as chlorine source to give the corresponding 3-aryl-3-chlorooxindoles in excellent yields and up to 93% enantiomeric excess. We have developed a highly effective asymmetric α-chlorination reaction of oxindoles by using an inexpensive cinchona alkaloid as the organocatalyst and N-chlorosuccinimide (NCS as the chlorination reagent under mild conditions, providing the corresponding 3-aryl-3-chlorooxindoles in excellent yields and up to 93% ee.
- Zhao, Mei-Xin,Zhang, Zhi-Wang,Chen, Ming-Xiao,Tang, Wen-Hao,Shi, Min
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experimental part
p. 3001 - 3008
(2011/06/28)
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- The palladium catalyzed asymmetric addition of oxindoles and allenes: An atom-economical versatile method for the construction of chiral indole alkaloids
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The Pd-catalyzed asymmetric allylic alkylation (AAA) is one of the most useful and versatile methods for asymmetric synthesis known in organometallic chemistry. Development of this reaction over the past 30 years has typically relied on the use of an ally
- Trost, Barry M.,Xie, Jia,Sieber, Joshua D.
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p. 20611 - 20622
(2012/02/01)
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- Direct N-carbamoylation of 3-monosubstituted oxindoles with alkyl imidazole carboxylates
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(Chemical Equation Presented) Regioselective N-carbamoylation of oxindoles was achieved through the use of imidazole carboxylate reagents. This reaction provides ready access to N-carbamoyl-3-monosubstituted oxindoles.
- Trost, Barry M.,Zhang, Yong,Zhang, Ting
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supporting information; experimental part
p. 5115 - 5117
(2009/10/24)
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- Highly enantioselective and organocatalytic α-amination of 2-Oxindoles
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Figur Presented An effective method for the asymmetric synthesis of 3-amino-2-oxindoles was developed. The tetrasubstituted chiral carbon center was generated by asymmetric amination of N-unprotected 2-oxindoles with azodicarboxylate catalyzed by commercial biscinchona alkaloids in good to excellent yields with high enantioselectivities.
- Cheng, Liang,Liu, Li,Wang, Dong,Chen, Yong-Jun
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supporting information; experimental part
p. 3874 - 3877
(2009/12/06)
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- Raney nickel-induced 3-alkylation of oxindole with alcohols and diols
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New reaction conditions are described, which turn Wenkert's synthesis of 3-alkyloxindoles (Raney nickel-induced alkylation of oxindole with alcohols) into a reproducible and highly efficient synthetic tool. The method is also extended to the preparation o
- Volk, Balázs,Mezei, Tibor,Simig, Gyula
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p. 595 - 597
(2007/10/03)
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- Preparation of indoles and oxindoles from N-(tert-butoxycarbonyl)-2-alkylanilines
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Treatment of dilithiated N-(tert-butoxycarbonyl)anilines 1 with dimethylformamide or carbon dioxide furnishes intermediates 3, 5, that are easily converted to N-(tert-butoxycarbonyl)indoles 4 and oxindoles (indol-2(3H)-ones, 7), respectively. Condensation of dilithiated 1 with N-methoxy-N-methylamides provides ketones 9 which are cyclized upon trifluoroacetic acid treatment to either 2-substituted 1-(tert-butoxycarbonyl)indoles 10 or 2-substituted indoles 11 depending on the reaction time. This general methodology has been applied to efficient synthesis of 1,2-alkyl-bridged indoles 12, 1,3,4,5-tetrahydrobenz[c,d]indole (16), 2a,3,4,5-tetrahydrobenz[c,d]indol-2(1H)-one (18), and 1-(tert-butoxycarbonyl)1H-pyrrolo[2,3-b]pyridine (21).
- Clark,Muchowski,Fisher,Flippin,Repke,Souchet
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p. 871 - 878
(2007/10/02)
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- Two New Oxindole Syntheses
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Two oxindole syntheses are described, both starting from ketones, in which the carbonyl carbon becomes C-3 of the oxindole.The first route uses o-lithioformanilide followed by attack with cyanide ion and hydrolysis.The second uses a pinacol-type rearragement (or the γ-silyl alcohol variation) to create the quaternary centre, and involves an intramolecular displacement of fluoride ion from an unactivated benzene ring by an amide nitrogen to complete the lactam ring.The two routes are stereochemically complementary, giving different spiro-oxindoles from norbornanone.
- Fleming, Ian,Loreto, Maria Antonietta,Wallace, Ian H.M.,Michael, Joseph P.
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p. 349 - 360
(2007/10/02)
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- Some Observations on the Brunner Reaction
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Elucidation of the stereochemical course of the Brunner reaction is described.A slight modification in the procedure gives better yields and seems very promising for a more general application of this reaction.
- Wolff, Jens,Taddei, Maurizio
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p. 4267 - 4272
(2007/10/02)
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- Photoinduced Cyclizations of Mono- and Dianions of N-Acyl-o-chloroanilines and N-Acyl-o-chlorobenzylamines as General Methods for the Synthesis of Oxindoles and 1,4-Dihydro-3(2H)-isoquinolinones
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Formation of the monoanions of a series of N-acyl-N-alkyl-o-chloroanilines by means of LDA in THF followed by irradiation with near-UV light affords 1,3-dialkyloxindoles in good yields.Similar photoinduced cyclizations of dianions derived from N-acyl-o-chloroanilines leads to 3-alkyloxindoles.Photocyclizations of mono- and dianion prepared from α,β-unsaturated o-haloanilides proceed to form 3-alkylideneoxindoles.Carbanions derived from N-acyl-o-chlorobenzylamines also undergo photoassisted ring closure to afford 1,4-dihydro-3(2H)-isoquinolinones.The influence of near-UV light and the effect of inhibitors implicate a radical-chain mechanism as the major reaction pathway in this convenient new method for oxindole and isoquinolinone synthesis.
- Goehring, R. Richard,Sachdeva, Yesh P.,Pisipati, Jyothi S.,Sleevi, Mark C.,Wolfe, James F.
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p. 435 - 443
(2007/10/02)
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