- Electrochemical Rearrangement of 3-Hydroxyoxindoles into Benzoxazinones
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We report an unexpected rearrangement of 3-hydroxyoxindoles into benzoxazinones using electrochemistry. Our reaction employs mild and environmentally friendly conditions, and the benzoxazinone products are obtained in moderate to excellent yields. Mechanistic experiments suggest that a peroxide intermediate is likely involved.
- Vayer, Marie,Pastor, Miryam,Kofink, Christiane,Maulide, Nuno
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supporting information
p. 27 - 32
(2022/01/15)
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- 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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- Counterion Control of t-BuO-Mediated Single Electron Transfer to Nitrostilbenes to Construct N-Hydroxyindoles or Oxindoles
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tert-Butoxide unlocks new reactivity patterns embedded in nitroarenes. Exposure of nitrostilbenes to sodium tert-butoxide was found to produce N-hydroxyindoles at room temperature without an additive. Changing the counterion to potassium changed the reaction outcome to yield solely oxindoles through an unprecedented dioxygen-transfer reaction followed by a 1,2-phenyl migration. Mechanistic experiments established that these reactions proceed via radical intermediates and suggest that counterion coordination controls whether an oxindole or N-hydroxyindole product is formed.
- Driver, Tom G.,Sung, Siyoung,Wink, Donald J.,Zadrozny, Joseph M.,Zhao, Yingwei,Zhu, Haoran
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supporting information
p. 19207 - 19213
(2021/08/09)
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- Kinetic Resolution of Tertiary Alcohols by Chiral DMAP Derivatives: Enantioselective Access to 3-Hydroxy-3-substituted 2-Oxindoles
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We developed an efficient acylative kinetic resolution of 3-hydroxy-3-substituted 2-oxindoles by a chiral DMAP derivative having a 1,1′-binaphthyl with two tert-alcohols units. A wide range of 3-hydroxy-3-substituted oxindoles having various functional groups were efficiently resolved (14 examples, up to s = 60) in the presence of 1 mol % of catalyst within 3-9 h. Multigram-scale reactions (10 g) also proceeded with a high s-factor (s = 43) within 5 h.
- Fujii, Kazuki,Mandai, Hiroki,Mitsudo, Koichi,Shiomoto, Ryuhei,Suga, Seiji
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supporting information
p. 1169 - 1174
(2021/01/13)
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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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- 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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- 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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- Chincona alkaloid-catalyzed enantioselective trifluoromethylthiolation of oxindoles
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An organocatalytic asymmetric trifluoromethylthiolation of 3-aryl or 3-alkyloxindoles employing a trifluoromethyl-substituted thioperoxide as the electrophilic trifluoromethylthiolating reagent was described. Reactions occurred in good to excellent enanti
- Yang, Tao,Shen, Qilong,Lu, Long
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supporting information
p. 678 - 680
(2014/10/16)
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- Enantioselective construction of tetrasubstituted stereogenic carbons through bronsted base catalyzed michael reactions: α′-hydroxy enones as key enoate equivalent
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Catalytic and asymmetric Michael reactions constitute very powerful tools for the construction of new C-C bonds in synthesis, but most of the reports claiming high selectivity are limited to some specific combinations of nucleophile/electrophile compound types, and only few successful methods deal with the generation of all-carbon quaternary stereocenters. A contribution to solve this gap is presented here based on chiral bifunctional Bronsted base (BB) catalysis and the use of α′-oxy enones as enabling Michael acceptors with ambivalent H-bond acceptor/donor character, a yet unreported design element for bidentate enoate equivalents. It is found that the Michael addition of a range of enolizable carbonyl compounds that have previously demonstrated challenging (i.e., α-substituted 2-oxindoles, cyanoesters, oxazolones, thiazolones, and azlactones) to α′-oxy enones can afford the corresponding tetrasubstituted carbon stereocenters in high diastereo- and enantioselectivity in the presence of standard BB catalysts. Experiments show that the α′-oxy ketone moiety plays a key role in the above realizations, as parallel reactions under identical conditions but using the parent α,β-unsaturated ketones or esters instead proceed sluggish and/or with poor stereoselectivity. A series of trivial chemical manipulations of the ketol moiety in adducts can produce the corresponding carboxy, aldehyde, and ketone compounds under very mild conditions, giving access to a variety of enantioenriched densely functionalized building blocks containing a fully substituted carbon stereocenter. A computational investigation to rationalize the mode of substrate activation and the reaction stereochemistry is also provided, and the proposed models are compared with related systems in the literature.
- Badiola, Eider,Fiser, Bla,Gmez-Bengoa, Enrique,Mielgo, Antonia,Olaizola, Iurre,Urruzuno, Iaki,Garca, Jess M.,Odriozola, Jos M.,Razkin, Jess,Oiarbide, Mikel,Palomo, Claudio
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supporting information
p. 17869 - 17881
(2015/02/19)
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- Palladium-catalyzed asymmetric allylic alkylation of 3-aryloxindoles with allylidene dipivalate: A useful enol pivalate product
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Triple A: The catalytic asymmetric allylic alkylation (AAA) of 3-aryloxindoles with allylidene dipivalate is described. This reaction affords stable, synthetically useful enol pivalates in high yield and with excellent regio- and enantioselectivity. A broad range of substrates is tolerated, including unprotected and 3-heteroaryl nucleophiles. Copyright
- Trost, Barry M.,Masters, James T.,Burns, Aaron C.
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supporting information
p. 2260 - 2264
(2013/03/28)
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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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- Facile synthesis of enantioenriched Cγ-tetrasubstituted α-amino acid derivatives via an asymmetric nucleophilic addition/protonation cascade
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Chemical equations presented. An asymmetric nucleophilic addition/protonation reaction of 3-substituted oxindoles and ethyl 2-phthalimidoacrylate has been described. This strategy can give direct access to Cγ-tetrasubstituted α-amino acid derivatives bearing 1,3-nonadjacent stereocenters with up to 98% yield, 94:6 dr, and >99% ee. Dual activation is proposed in the transition state, and the opposite enantiomers can be obtained simply by changing cinchonidine-derived catalyst to the cinchonine analogue.
- Duan, Shu-Wen,An, Jing,Chen, Jia-Rong,Xiao, Wen-Jing
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supporting information; experimental part
p. 2290 - 2293
(2011/06/22)
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- Catalytic enantioselective fluorination of oxindoles
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We have developed a highly efficient catalytic enantioselective fluorination of oxindole derivatives. In the presence of a catalytic amount of chiral Pd complex 2 (2.5 mol %), various substrates, including aryl- and alkyl-substituted oxindoles, were fluor
- Hamashima, Yoshitaka,Suzuki, Toshiaki,Takano, Hisashi,Shimura, Yuta,Sodeoka, Mikiko
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p. 10164 - 10165
(2007/10/03)
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- 3-3-DI-SUBSTITUTED-OXINDOLES AS INHIBITORS OF TRANSLATION INITIATION
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Compositions and methods for inhibiting translation using 3-(5-tert-Butyl-2-Hydroxy-phenyl)-3-phenyl-1,3-dihydro-indol-2-one and/or its derivatives are provided. Compositions, methods and kits for treating (1) cellular proliferative disorders, (2) non-proliferative, degenerative disorders, (3) viral infections, and/or (4) disorders associated with viral infections, using 3-(5-tert-butyl-2-hydroxy-phenyl)-3-phenyl-1,3-dihydro-indol-2-one and/or its derivatives are described.
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Page/Page column 28; 35
(2008/06/13)
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