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Easy access to 3-indolyl 1,1,2,2-ethanetetracarboxylates from malonates and indoles catalyzed by Pd(OAc)2

A novel dehydrodimerization of malonates with indoles has been developed, providing simple and rapid access to 3-indolyl tetramethyl 1,1,2,2-ethanetetracarboxylates. Pd(OAc)2-catalyzed ?one pot? C(sp2)?C(sp3) and C(sp3)?C(sp3) cross-dehydrogenative-couplings of malonates with a variety of 2-aryl indoles were involved. The titled compounds were obtained in high yields with good functional group tolerance.

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Quinoxaline – Wikipedia,
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Enatioselective Synthesis of Tetrahydrocarbazoles via Chiral Phosphoric Acid Promoted Domino Friedel?Crafts-type Reaction of Indole-3-butanal with Indoles

By employing a chiral phosphoric acid as a catalyst, enantioselective domino Friedel?Crafts-type reaction of indole-3-butanal with indoles was realized. This transformation allowed for the synthesis of a wide variety of enantioenriched 1-indolyl-tetrahydrocarbazoles with good yields (up to 99%) in moderate enantioselectivities (up to 81% ee).

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Oxidation of 2-arylindoles for synthesis of 2-arylbenzoxazinones with oxone as the sole oxidant

A novel and efficient method for the oxidation of 2-arylindoles to synthesize 2-arylbenzoxazinones utilizing oxone as the sole oxidant has been developed. The reaction tolerates a wide range of functional groups and allows quick and atom-economical assembly of a variety of valuable 2-arylbenzoxazinones in high yields.

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Quinoxaline – Wikipedia,
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New Indole Tubulin Assembly Inhibitors Cause Stable Arrest of Mitotic Progression, Enhanced Stimulation of Natural Killer Cell Cytotoxic Activity, and Repression of Hedgehog-Dependent Cancer

We designed 39 new 2-phenylindole derivatives as potential anticancer agents bearing the 3,4,5-trimethoxyphenyl moiety with a sulfur, ketone, or methylene bridging group at position 3 of the indole and with halogen or methoxy substituent(s) at positions 4-7. Compounds 33 and 44 strongly inhibited the growth of the P-glycoprotein-overexpressing multi-drug-resistant cell lines NCI/ADR-RES and Messa/Dx5. At 10 nM, 33 and 44 stimulated the cytotoxic activity of NK cells. At 20-50 nM, 33 and 44 arrested >80% of HeLa cells in the G2/M phase of the cell cycle, with stable arrest of mitotic progression. Cell cycle arrest was followed by cell death. Indoles 33, 44, and 81 showed strong inhibition of the SAG-induced Hedgehog signaling activation in NIH3T3 Shh-Light II cells with IC50 values of 19, 72, and 38 nM, respectively. Compounds of this class potently inhibited tubulin polymerization and cancer cell growth, including stimulation of natural killer cell cytotoxic activity and repression of Hedgehog-dependent cancer.

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Quinoxaline – Wikipedia,
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Ruthenium-Catalyzed Selective C?C Coupling of Allylic Alcohols with Free Indoles: Influence of the Metal Catalyst

Versatile reactive activities of allyl alcohols with free indoles in C?H functionalization reactions were investigated. Direct alkylation or cascade cyclization reactions could be selectively controlled based on the catalyst system: Ru(PPh3)3Cl2 provided C3-substituted beta-ketone indoles whereas [Ru(p-cymene)Cl2]2 yielded cyclized indoles.

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Quinoxaline – Wikipedia,
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Direct oxidative dearomatization of indoles: Access to structurally diverse 2,2-disubstituted indolin-3-ones

Described is an efficient oxidative dearomatization of indoles with TEMPO oxoammonium salt and a broad range of nucleophiles. Under very mild conditions, dearomative oxyalkynylation and oxyalkenylation of indoles to structurally diverse 2,2-disubstituted indolin-3-ones were developed for the first time with high atom-economy. In addition, dearomative oxyarylation, oxyallylation, and oxycyanation of indoles were also demonstrated. Mechanism studies indicated that TEMPO oxoammonium salt served as the sole oxidant source through an electron donor-acceptor (EDA) intermediate.

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Synthesis of some bisindolyl analogs for in vitro cytotoxic and DNA cleavage studies

One-pot, three components, conventional and microwave-assisted synthesis of bisindolyl analogs is described. Michael addition of preformed 2,5-disubstituted indole-3-carboxaldehydes and 3-methyl-1H-pyrazol-5(4H)-one with 2,5-disubstituted indoles under solvent and catalyst-free conditions afforded the hitherto unreported 2,5-disubstituted bisindolyl analogs bearing a pyrazolone moiety in excellent yields. All the synthesized compounds were characterized using IR, 1H NMR, mass spectral, and analytical data. The analogs were screened for in vitro cytotoxic and DNA cleavage studies. Among the screened compounds 4c, 4f, and 4h-4j have emerged as most potent cytotoxic and 4c and 4f-4h as active DNA cleavage analogs.

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Quinoxaline – Wikipedia,
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Catalytic Asymmetric Mukaiyama-Mannich Reaction of Cyclic C-Acylimines with Difluoroenoxysilanes: Access to Difluoroalkylated Indolin-3-ones

A catalytic enantioselective Mukaiyama-Mannich reaction of cyclic C-acylimines with difluoroenoxysilanes is reported. (S)-TRIP enables the enantioselective synthesis of a series of novel difluoroalkylated indolin-3-ones bearing a quaternary stereocenter in up to 97% yield and 98% ee. The synthetic utility of this protocol is highlighted by efficient conversion of the products to the corresponding indolin-3-one derivatives without any erosion of the enantiopurity.

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The invention discloses a method for synthesis of indole with the nitrile is straight, is characterized in that in order to 2 – iodo toluene derivatives as the substrate, the anhydrous copper sulfate and potassium tertiary butyl alcohol, nitrile derivatives with 2 – iodo toluene derivatives mol ratio of 0.02 – 0.1: 2 – 4:5 – 20:1, in the solvent for 60 – 105 C reaction 4 – 48 h, petroleum ether/dichloromethane/ethyl acetate according to volume 20 – 5:10: 1 mixed as eluant, over silica gel column separation, to obtain the target product. The method of the invention the operation is simple, mild condition, the yield is high, it is a green novel synthetic method. (by machine translation)

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The solid-state reaction between anilines and phenacyl bromides in the presence of an equimolecular amount of sodium bicarbonate gives N-phenacylanilines. Microwave irradiation of mixtures of these compounds with anilinium bromides at 540 W for 45-60 s provides a mild, general, and environmentally friendly method for the synthesis of 2-arylindoles in 50-56% overall yields. A one-pot variation of the method, involving irradiation of 2:1 mixtures of anilines and phenacyl bromides, was also developed, allowing a simplified experimental procedure and leading to improved yields (52-75%). Georg Thieme Verlag Stuttgart.

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