- Cobalt-Catalyzed Dearomatization of Indoles via Transfer Hydrogenation to Afford Polycyclic Indolines
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A cobalt-catalyzed dearomatization of indoles via transfer hydrogenation with HBpin and H2O has been developed. This reaction offered a straightforward platform to access hexahydropyrido[1,2-a]indoles in high regio- and chemoselectivity. A preliminary reaction mechanism was proposed on the basis of deuterium-labeling experiments, and a cobalt hydride species was involved in the reaction.
- Chen, Siwei,Cai, Min,Huang, Junru,Yao, Hequan,Lin, Aijun
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supporting information
p. 2212 - 2216
(2021/04/05)
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- Decarboxylation of indole-3-carboxylic acids under metal-free conditions
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Two reaction systems have been developed for the decarboxylation of indole-3-carboxylic acids. The decarboxylation can be achieved smoothly under K2CO3-catalyzed or acetonitrile-promoted basic conditions. It provided an efficient and simple method for the transformation of indole-3-carboxylic acids and the corresponding indoles were isolated with good to excellent yields. From the experimental facts, we put forward the possible reaction mechanism.
- Chen, Xia,Zhou, Xiao-Yu
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supporting information
p. 805 - 812
(2020/02/20)
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- Palladium-Catalyzed Oxidation-Hydroxylation and Oxidation-Methoxylation of N -Boc Indoles for the Synthesis of 3-Oxoindolines
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The palladium-catalyzed oxidation-hydroxylation and oxidation-methoxylation of N -Boc indoles for the synthesis of tert -butyl 2-hydroxy(methoxy)-3-oxoindoline-1-carboxylates and their derivatives is developed. The process occurs readily using PdCl 2 as the catalyst and acetonitrile as the solvent to afford 3-oxoindolines in moderate to high yields. A mechanism for this Pd-catalyzed oxidation-hydroxylation and oxidation-methoxylation of N -Boc indoles is proposed.
- Zhou, Xiao-Yu,Chen, Xia,Wang, Liang-Guang,Yang, Dan,Li, Zhi
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p. 3662 - 3669
(2017/08/15)
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- Method for preparing indole and derivatives thereof
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The invention discloses a method for preparing indole and derivatives of indole. The method for preparing indole and the derivatives of indole is characterized by comprising the following two steps that (1) a catalyst, a ligand and alkali are added in a reaction tube, under the protection of nitrogen, beta-hydroxy ketone or ester is reacted with a mixed solution of o-nitro aryl halides for 3 to 8h in an oil bath pan at the temperature of 90 to 120 DEG C, and then cooled to room temperature after reaction, and extracted, washed, dried and subjected to chromatography to obtain a product of o-nitro alpha-aryl ketone or ester; (2) o-nitro alpha-aryl ketone or ester obtained in the step (1), a reducing agent system and a solvent are added to the reaction tube, and reacted for 3 to 8h at the temperature of 60 to 100 DEG C, and then extracted, washed, dried and subjected to chromatography after being reacted to obtain a target product of indole and the derivatives of indole. Reaction raw materials, the catalyst, the ligand, the alkali and the solvent used in the invention are all industrial commodities, and simple and readily available, wide in sources, cheap in price, and further very stable in performances, and with no need for special storage conditions; in addition, the method for preparing indole and the derivatives of indole disclosed by the invention has the characteristics of low cost, high yield, simple process, less pollution and the like.
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- Divergent synthesis of indoles, oxindoles, isocoumarins and isoquinolinones by general Pd-catalyzed retro-aldol/α-arylation
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Divergent synthesis of indoles, oxindoles, isocoumarins and isoquinolinones is described in this report by using a general Pd-catalyzed tandem reaction of β-hydroxy carbonyl compounds with aryl halides bearing an ortho-nitro, -ester or -cyano substituent. A key retro-aldol/α-arylation reaction is involved that merges classic Pd cross-coupling chemistry with novel Pd-promoted retro-aldol C-C activation to produce α-arylated ketones or esters. Subsequent intramolecular condensation of the carbonyl with the ortho-synthon gives target heterocycles. The use of common, commercially available and cheap substrates and catalyst system adds additional synthetic advantages to the conceptual significance.
- Zhang, Song-Lin,Yu, Ze-Long
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p. 10511 - 10515
(2016/11/18)
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- Discovery of a First-in-Class, Potent, Selective, and Orally Bioavailable Inhibitor of the p97 AAA ATPase (CB-5083)
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The AAA-ATPase p97 plays vital roles in mechanisms of protein homeostasis, including ubiquitin-proteasome system (UPS) mediated protein degradation, endoplasmic reticulum-associated degradation (ERAD), and autophagy. Herein we describe our lead optimization efforts focused on in vitro potency, ADME, and pharmaceutical properties that led to the discovery of a potent, ATP-competitive, D2-selective, and orally bioavailable p97 inhibitor 71, CB-5083. Treatment of tumor cells with 71 leads to significant accumulation of markers associated with inhibition of UPS and ERAD functions, which induces irresolvable proteotoxic stress and cell death. In tumor bearing mice, oral administration of 71 causes rapid accumulation of markers of the unfolded protein response (UPR) and subsequently induces apoptosis leading to sustained antitumor activity in in vivo xenograft models of both solid and hematological tumors. 71 has been taken into phase 1 clinical trials in patients with multiple myeloma and solid tumors.
- Zhou, Han-Jie,Wang, Jinhai,Yao, Bing,Wong, Steve,Djakovic, Stevan,Kumar, Brajesh,Rice, Julie,Valle, Eduardo,Soriano, Ferdie,Menon, Mary-Kamala,Madriaga, Antonett,Kiss Von Soly, Szerenke,Kumar, Abhinav,Parlati, Francesco,Yakes, F. Michael,Shawver, Laura,Le Moigne, Ronan,Anderson, Daniel J.,Rolfe, Mark,Wustrow, David
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p. 9480 - 9497
(2016/01/12)
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- 3-(o-Trifluoroacetamidoaryl)-1-propargylic esters: common intermediates for the palladium-catalyzed synthesis of 2-aminomethyl-, 2-vinylic, and 2-alkylindoles
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3-(o-Trifluoroacetamidoaryl)-1-propargylic esters have been used as common synthetic intermediates for the preparation of a variety of 3-unsubstituted 2-substituted indoles. Treating ethyl 3-(o-trifluoroacetamidoaryl)-1-propargylic carbonates unsubstituted or containing an aryl substituent at the propargylic carbon with piperazines and Pd(PPh3)4 in THF at 80 °C affords 2-(piperazin-1-ylmethyl)indoles in excellent yields. Good to excellent yields of 2-aminomethylindoles are also obtained with other secondary amines. Ethyl 3-(o-trifluoroacetamidoaryl)-1-propargylic carbonates bearing an alkyl substituent at the propargylic carbon and ethyl 3-(o-trifluoroacetamidoaryl)-1-propargylic acetates disubstituted at the propargylic carbon give 2-vinylic indoles with the Pd(OAc)2/PPh3 combination and Et3N in THF at 80 °C. Formation of 2-vinylic indoles is quite stereoselective, generating trans vinylic derivatives, at least with the substrates that we have investigated. In the presence of formic acid, Et3N, and Pd(PPh3)4 in MeCN at 80 °C, ethyl 3-(o-trifluoroacetamidoaryl)-1-propargylic carbonates afford 2-alkylindoles in good to excellent yields.
- Ambrogio, Ilaria,Cacchi, Sandro,Fabrizi, Giancarlo,Prastaro, Alessandro
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scheme or table
p. 8916 - 8929
(2009/12/07)
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- Pd PEPPSI-IPr-mediated reactions in metal-coated capillaries under MACOS: The synthesis of indoles by sequential aryl amination/heck coupling
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A method has been devised for the microwave-assisted, continuous-flow preparation of indole alkaloids by a two-step aryl amination/cross-coupling sequence of bromoalkenes and 2-bromoanilines. This process requires both the presence of a metal-lined flow tube (a 1180 micron capillary) and the Pd PEPPSI-IPr catalyst; without either, the catalyst or the film, there is zero turnover of this catalytic process. A silver film has been shown to provide some conversion (48-62%), but optimal results (quantitative) across a variety of bromoalkenes and bromoanilines were achieved by using a highly porous palladium film. Possible roles for the Pd film are considered, as is the interplay of the catalyst and the film.
- Shore, Gjergji,Morin, Sylvie,Mallik, Debasis,Organ, Michael G.
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p. 1351 - 1356
(2008/09/17)
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- 2-Alkylindoles via palladium-catalyzed reductive cyclization of ethyl 3-(o-trifluoroacetamidophenyl)-1-propargyl carbonates
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The reaction of ethyl 3-(o-trifluoroacetamidophenyl)-1-propargyl carbonates with formate anions in the presence of Pd(PPh3)4 affords 2-alkylindoles in good to excellent yields.
- Ambrogio, Ilaria,Cacchi, Sandro,Fabrizi, Giancarlo
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p. 7721 - 7725
(2008/03/30)
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- Ruthenium-catalyzed heteroannulation of anilines with alkanolammonium chlorides leading to indoles
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Anilines react with alkanolammonium chlorides in an aqueous medium (H2O-dioxane) at 180°C in the presence of a catalytic amount of a ruthenium catalyst together with SnCl2·2H2O to afford the corresponding indoles in moderate to good yields. Especially, when triisopropanolammonium chloride is employed to react with anilines, 2-methylindoles are formed regioselectively. The presence of SnCl2·2H2O is necessary for the effective formation of indoles. A reaction pathway involving alkanol group transfer from alkanolamines to anilines, N-alkylation of anilines by anilinoalkanols and heteroannulation of 1,2-dianilinoalkanes is proposed for this catalytic process.
- Cho, Chan Sik,Kim, Jin Hwang,Kim, Tae-Jeong,Shim, Sang Chul
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p. 3321 - 3329
(2007/10/03)
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- Ruthenium-catalyzed synthesis of indoles from anilines and trialkanolammonium chlorides in an aqueous medium
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Anilines react with trialkanolammonium chlorides in an aqueous medium (H2O-dioxane) at 180°C in the presence of a catalytic amount of ruthenium(III) chloride hydrate and triphenylphosphine together with tin(II) chloride dihydrate to afford the corresponding indoles in good yields. (C) 2000 Elsevier Science Ltd.
- Cho, Chan Sik,Kim, Jin Hwang,Shim, Sang Chul
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p. 1811 - 1814
(2007/10/03)
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- Ruthenium-catalysed synthesis of indoles from anilines and trialkanolamines in the presence of tin(II) chloride dihydrate
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Anilines react with trialkanolamines in dioxane in the presence of a catalytic amount of a ruthenium catalyst together with tin(II) chloride dihydrate to give the corresponding indoles in moderate to good yields.
- Cho, Chan Sik,Lim, Hyo Kyun,Shim, Sang Chul,Kim, Tae Jeong,Choi, Heung-Jin
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p. 995 - 996
(2007/10/03)
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- Substituted N-aryl alk-1-enesulfinamides: Preparation, properties and conversion into the corresponding indole compounds [1]
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Reaction of vinylic organometallic derivatives with N-sulfinyl arenamines 2 affords the title sulfinamides 3. On heating their solutions in selected solvents to 80-124 °C, these sulfinamides are converted into the corresponding indoles 6, probably via a [3.3]-sigmatropic rearrangement to intermediates VIII which undergo an intramolecular carbophilic reaction of the nitrogen atom with the neighboring sulfine group, followed by elimination of HSOH. The triethyloxonium tetrafluoroborate- or boron trifluoride etherate catalyzed conversion 3 → 6 can be carried out at a much lower temperature. Elsevier,.
- Baudin, Jean-Bernard,Commenil, Marie-Gabrielle,Julia, Sylvestre A.,Lorne, Robert,Mauclaire, Laurent
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p. 329 - 350
(2007/10/03)
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- Electrophilic Heteroaromatic Substitutions: Reactions of 5-X-Substituted Indoles with 4,6-Dinitrobenzofuroxan
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The SEAr substitutions of a number of 5-X-substituted indoles (1a-f), 5-X-substituted 2-methylindoles (1g-j) and N-methylindole (1k) by 4,6-dinitrobenzofuroxan (DNBF) have been kinetically studied in 70-30 (v/v) H2O-Me2SO, 50-50 (v/v) H2O-Me2SO, methanol and acetonitrile.The absence of a significant dependence of the rates of reactions on the hydrogen or deuterium labelling at C-3 of the indole ring indicates that electrophilic attack (k1DNBF) by DNBF at this position is the rate-limiting step of the substitutions.However, the k1DNBF rate constants are strongly sensitive to the solvent polarity, the observed reactivity sequence being 70-30 H2O-Me2SO > 50-50 H2O-Me2SO > methanol > acetonitrile.This trend is consistent with a highly dipolar transition state where the development of negative charge in the DNBF moiety is concomitant with that of a partial positive charge on the indole nitrogen.The finding of relatively large negative ρ values (-3.85) for the Hammett plots log k1DNBF = f(?px supports this idea.An interesting result is that the effect of the X substituent on the rates (k1DNBF) is the same in the four solvents studied and does not depend upon the substitution at C-2 of the indole ring.However, the Broensted or Hammett lines for the 5-X-2-methylindoles are located about 1.5 log k unit below those for the 5-X-indoles in a given solvent, showing that the 2-methyl group causes significant steric hindrance to the approach of DNBF from the adiacent C-3 position.Rates of protiodetritiation of a large number of indoles have also been measured in aqueous solution.The data define a unique Broensted line (βlnH = 0.65), implying that the 2-substituents do not exert any steric effect on the rates of the exchange process and suggesting that the correlation can be used to estimate unknown pKa values of indoles with a free 3-position.Comparison of the rates of coupling of indoles with 4,6-dinitrobenzofuroxan with similar data for coupling of these heterocycles with p-nitrobenzenediazonium cation reveals that, despite its neutral character, DNBF is the most electrophilic species.DNBF also appears to be a much stronger electrophile than the proton.
- Terrier, Francois,Pouet, Marie-Jose,Halle, Jean-Claude,Hunt, Stephen,Jones, John R.,Buncel, Erwin
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p. 1665 - 1672
(2007/10/02)
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- SYNTHESIS OF INDOLES FROM N-ARYL-1-ALKENYLSULPHINAMIDES
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Reactions of 1-alkenylmagnesium bromides with N-sulphinyl-benzenamines affords the title sulphinamides 5.On heating in toluene, these sulphonamides 5 are the transformed into the corresponding indoles.
- Baudin, Jean-Bernard,Julia, Sylvestre A.
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p. 837 - 840
(2007/10/02)
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- Indole Synthesis via SRN1 Reactions
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o-Haloanilines react with ketone enolate ions in ammonia under irradiation to form indoles in good yields.
- Bard, Raymond R.,Bunnett, Joseph F.
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p. 1546 - 1547
(2007/10/02)
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