- Iron-Catalyzed Amination of Strong Aliphatic C(sp3)-H Bonds
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A concept for intramolecular denitrogenative C(sp3)-H amination of 1,2,3,4-tetrazoles bearing unactivated primary, secondary, and tertiary C-H bonds is discovered. This catalytic amination follows an unprecedented metalloradical activation mechanism. The utility of the method is showcased with the short synthesis of a bioactive molecule. Moreover, an initial effort has been embarked on for the enantioselective C(sp3)-H amination through the catalyst design. Collectively, this study underlines the development of C(sp3)-H bond functionalization chemistry that should find wide application in the context of drug discovery and natural product synthesis.
- Das, Sandip Kumar,Roy, Satyajit,Khatua, Hillol,Chattopadhyay, Buddhadeb
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p. 16211 - 16217
(2020/10/26)
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- Palladium-metalated porous organic polymers as recyclable catalysts for chemoselective decarbonylation of aldehydes
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A novel palladium nanoparticle (NP)-metalated porous organic ligand (Pd NPs/POL-xantphos) has been prepared for the chemoselective decarbonylation of aldehydes. This heterogenous catalyst not only has excellent catalytic activity and chemoselectivity, but also holds high activity after 10 runs of reuse. The effective usage of this method is demonstrated through the synthesis of biofuels such as furfuryl alcohol (FFA) via the highly chemoselective decarbonylation of biomass-derived 5-hydroxy-methylfurfural (HMF) with a TON up to 1540. More importantly, 9-fluorenone could be obtained in one step through the decarbonylation of 2-bromobenzaldehyde by using this heterogeneous catalyst.
- Li, Wen-Hao,Li, Cun-Yao,Li, Yan,Tang, Hai-Tao,Wang, Heng-Shan,Pan, Ying-Ming,Ding, Yun-Jie
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supporting information
p. 8446 - 8449
(2018/08/28)
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- Synthesis method of 5-bromo-7-azaindole
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The invention relates to a synthesis method of 5-bromo-7-azaindole. With 7-azaindole as a raw material, conjugation of the five-membered ring of indole is damaged by low-pressure liquid-phase hydrogenation, and a key medical intermediate 5-bromo-7-azaindole is prepared through oxybromination and nonmetal oxydehydrogenation. The product purity is higher than or equal to 99%. Bromine atoms are introduced by an oxybromination technology, the utilization rate of the bromine atoms exceeds 98%, the use of bromine is avoided, and the problem that a large amount of bromine-containing waste liquid is generated in original technology is solved. According to the synthesis method provided by the invention, through nonmetal catalytic dehydrogenation, heavy metal catalysis is avoided, the problem of heavy metal residue easily occurring in the product is solved, and the safety of medicine products is ensured. The reaction efficiency can be effectively improved, the reaction time is shortened, and thetotal reaction yield is increased; moreover, industrial waste liquid and residue is reduced, industrial popularization is facilitated, and remarkably high economic benefits are created.
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Paragraph 0043-0047; 0058-0063; 0075-0079
(2018/06/26)
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- Sustainable Radical Cascades to Synthesize Difluoroalkylated Pyrrolo[1,2-a]indoles
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We disclose herein a photocatalytic difluoroalkylation and cyclization cascade reaction of N-(but-2-enoyl)indoles with broad substrate scopes in up to 90% isolated yield. This method provides sustainable and efficient access to synthesize difluoroalkylated pyrrolo[1,2-a]indoles with a quaternary carbon center under mild conditions.
- Huang, Honggui,Yu, Menglin,Su, Xiaolong,Guo, Peng,Zhao, Jia,Zhou, Jiabing,Li, Yi
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p. 2425 - 2437
(2018/02/23)
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- Synthesis method of 5-chloro-7-azaindole
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The invention provides a synthesis method of 5-chloro-7-azaindole. The synthesis method comprises the following steps: (1) reacting a dilithium initiator and trimethylbromosilane to prepare silicon-containing organic lithium; (2) reacting 2-amino-3-methylpyridine and di-tert-butyl dicarbonate to prepare 2-N-BOC-amino-3-methylpyridine; (3) performing lithiation on the 2-N-BOC-amino-3-methylpyridine through the silicon-containing organic lithium, and performing delithiation activation, cyclization and dehydration to prepare 7-azaindole; (4) performing hydrogenation reduction reaction on the 7-azaindole to generate 2,3-dihydro-7-azaindole; (5) performing chlorination reaction on the 2,3-dihydro-7-azaindole through liquid chlorine to generate 5-chloro-2,3-dihydro-7-azaindole; and (6) performing dehydrogenation reaction on the 5-chloro-2,3-dihydro-7-azaindole to obtain 5-chloro-7-azaindole. The synthesis method provided by the invention has the advantages of mild conditions and high yield.
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- α-Halo Amides as Competent Latent Enolates: Direct Catalytic Asymmetric Mannich-Type Reaction
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α-Halogenated carbonyl compounds are susceptible to dehalogenation and thus largely neglected as enolate precursors in catalytic enantioselective C-C bond-forming reactions. By merging the increased stability of the α-C-halogen bond of amides and the direct enolization methodology of the designed amide, we explored a direct catalytic asymmetric Mannich-type reaction of α-halo 7-azaindoline amides with N-carbamoyl imines. All α-halo substituents, α-F, -Cl, -Br, -I amides, were tolerated to provide the Mannich-adducts in a highly stereoselective manner without undesirable dehalogenation. The diastereoselectivity switched intriguingly depending on the substitution pattern of the aromatic imines, which is ascribed to stereochemical differentiation based on the open transition-state model. Functional group interconversion of the 7-azaindoline amide moiety of the Mannich-adducts and further elaboration into a diamide without dehalogenation highlight the synthetic utility of the present protocol for accessing enantioenriched halogenated chemical entities.
- Sun, Bo,Balaji, Pandur Venkatesan,Kumagai, Naoya,Shibasaki, Masakatsu
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supporting information
p. 8295 - 8301
(2017/06/27)
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- Production process of 5-bromo-7-azaindole
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The invention relates to a production process of 5-bromo-7-azaindole. The production process includes following steps: (1), using 7-azaindole as a raw material, and enabling 7-azaindole to be in catalytic hydrogenation under action of a catalyst-palladium loaded mesoporous carbon to generate dihydro-7-azaindole; (2), enabling dihydro-7-azaindole to be in bromination reaction under action of hydrogen bromide and hydrogen peroxide to generate dihydro-5-bromo-7-azaindole, where a feeding molar ratio of dihydro-7-azaindole, hydrogen bromide and hydrogen peroxide is 1:10-30:1-2, and temperature for bromination reaction is 20-30 DEG C; (3), enabling dihydro-5-bromo-7-azaindole to be in oxidative dehydrogenation under action of manganese dioxide/glacial acetic acid to generate 5-bromo-7-azaindole. The production process has the advantages of high reaction yield and low cost.
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Paragraph 0016
(2017/04/27)
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- Synthesis method of 5-bromo-7-azaindole
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The invention discloses a synthesis method of 5-bromo-7-azaindole. With 7-azaindole as the raw material, hydrogenation reduction, bromination and dehydrogenation are conducted, a platinum-carbon catalyst is added for catalyzing 7-azaindole to conduct hydrogenation to prepare dihydro-7-azaindole, catalysis efficiency is improved, and reaction energy consumption and reaction time are decreased; 5-bromo-7-azaindoline is synthesized by adding sodium bromide for catalysis, a mixture of chromic oxide, zinc oxide and magnesium oxide is added for substituting manganese dioxide for catalytic dehydrogenation reaction, reaction time can be effectively shortened, and reaction yield is increased. By means of the method, reaction efficiency can be effectively improved, reaction time is shortened, the total reaction yield is increased, process waste liquid and waste slag are reduced, industrial popularization is facilitated, and extremely high economic benefits are achieved.
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Paragraph 0142; 0143; 0144; 0145
(2016/12/01)
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- A 5-bromo-7-aza-indole synthesis process (by machine translation)
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This invention relates to a kind of 5-bromo-7-aza-indole synthesis process, the steps of: the 7-aza indole, Raney nickel, ethanol stirring and hydrogen; reacting filtering, the filter cake is washed with ethanol washing, combined filtrate, concentrated dry, be 7-aza indole [...] ; the crude product with toluene-P-sulfonic acid, methylene chloride mixed, and stirring instillment bromide ; sodium hyposulfite washing the reaction solution, the organic phase is dried with anhydrous sodium sulfate, concentrated to obtain 5-bromo-7-aza-indoline product; the product is dissolved in toluene, adding manganese dioxide, heating reflux reaction; filtering the reaction liquid, the filter cake washed with methylene chloride, combined organic phase, dried, concentrated to obtain 5-bromo-7-azaindoles crude, PE/EA mixed solution for crystallization to obtain the finished product. The invention has the advantages of low cost, simple process, the operation is simple, and the like, is suitable for large-scale factory production, this method generating the purity of the product in 99% or more, the yield of 74% or more, comprehensive utilization rate is high. (by machine translation)
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Paragraph 0016
(2017/03/08)
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- AZAINDOLE GLUCOKINASE ACTIVATORS
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Provided herein are compounds of the formula (I): as well as pharmaceutically acceptable salts thereof, wherein the substituents are as those disclosed in the specification. These compounds, and the pharmaceutical compositions containing them, are useful for the treatment of metabolic diseases and disorders such as, for example, type II diabetes mellitus.
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Page/Page column 16
(2011/06/26)
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- GPR 119 MODULATORS
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Compounds of Formula (I) that modulate the activity of the G -protein-coupled receptor GPFM 19 and their uses in the treatment of diseases linked to the modulation of the G-protein-coupled receptor GPR119 in animals are described herein.
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Page/Page column 61-62
(2010/11/18)
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- 7-azaindol-3-ylacrylamides active as kinase inhibitors
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Compounds represented by Formula (I) wherein R1 and R2 are as defined in the specification, compositions thereof, and methods of use thereof.
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Page/Page column 100-101
(2009/07/10)
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- NOVEL ANTIMALARIA AGENT CONTAINING HETEROCYCLIC COMPOUND
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Disclosed is an antimalarial agent containing a compound represented by the formula: [wherein A1 represents a 3-pyridyl group that may have a substituent, a 6-quinolyl group that may have a substituent, or the like; X1 represents a group represented by the formula -C(=O)-NH- or the like; E represents a furyl group, a thienyl group or a phenyl group; with the proviso that A1 may have one to three substituents, and E has one of two substituents] or a salt thereof or hydrates thereof.
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Page/Page column 60-63
(2008/06/13)
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- INDOLE DERIVATIVES
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The invention concerns indole derivatives of Formula (I) or pharmaceutically-acceptable salts thereof, wherein each of Ring A, m, R1, R2, n, R3 and G1 has any of the meanings defined hereinbefore in the description; processes for their preparation, pharmaceutical compositions containing them and their use in therapy, for example in the treatment of disease mediated by a PI3K enzyme and/or a mTOR kinase.
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Page/Page column 80
(2008/06/13)
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- NOVEL ANTIFUNGAL AGENT COMPRISING HETEROCYCLIC COMPOUND
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The present invention provides an antifungal agent represented by the formula: [wherein A1 represents a 3-pyridyl group which may have a substituent, a quinolyl group which may have a substituent, or the like; X1 represents a group represented by the formula -NH-C(=O)-, a group represented by the formula -C(=O)-NH-, or the like; E represents a furyl group, a thienyl group, a pyrrolyl group, a phenyl group, a pyridyl group, a tetrazolyl group, a thiazolyl group or a pyrazolyl group; with the proviso that A1 may have 1 to 3 substituents, and E has one or two substituents].
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Page/Page column 68; 70-71
(2010/11/08)
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- A practical, efficient synthesis of 5-amino-7-azaindole
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A much improved, workable synthesis of 5-amino-7-azaindole is described in 66% overall yield starting from 2-amino-5-nitropyridine. The key stage involves a microwave promoted heteroannulation reaction of a pyridine alkyne. Georg Thieme Verlag Stuttgart.
- Pearson, Stuart E.,Nandan, Santosh
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p. 2503 - 2506
(2007/10/03)
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- SYNTHESIS
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The present invention provides a novel substituted azaindoline intermediate of formula (I) and a method for its synthesis. The novel substitued azaindoline intermediate (I) is provided for use in the manufacture of 5-substituted 7-azaindolines and 5-substituted 7-azaindoles.
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Page 32; 48-49
(2010/02/08)
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- Excited-state amine-imine double proton transfer in 7-azaindoline
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Ground-state thermodynamics and excited-state amine/imine tautomerism in 7-azaindoline (7AZD) mediated by hydrogen bond formation have been studied by means of absorption and emission spectroscopies. The association constants in cyclohexane (298 K) were determined to be 80, 2.5 × 102, and 7.8 × 102 M-1, for the formation of 7AZD dimer, 7AZD/azacyclohexanone, and 7AZD/acetic acid dual hydrogen-bonded complexes, respectively. The 7AZD/acetic acid complex undergoes a fast (? 3 × 109 s-1) excited-state double proton transfer (ESDPT) reaction, resulting in a prominent imine-like tautomer emission. Proton-transfer isomers of 7AZD have been identified through syntheses and spectral characterization of various 7AZD methyl derivatives. In contrast, ESDPT is prohibited in cases of 7AZD dimer and 7AZD/azacyclohexanone hydrogen-bonded complex. The results, in combination with a comparative study on 7-azaindole, generalize the amine/imine tautomerism, which can be fine-tuned by the length of π electron conjugation coupled with types of associated guest molecules, further supporting the proposed catalytic-versus-noncatalytic model for the ESDPT reaction.
- Chou, Pi-Tai
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p. 7818 - 7829
(2007/10/03)
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- NOVEL INTRAMOLECULAR DIELS-ALDER REACTIONS OF PYRIMIDINES. SYNTHESIS OF HETEROCYCLIC ANNELATED PYRIDINES
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Pyrimidines carrying a dienophilic side-chain at the 2 or 5 position undergo intramolecular Diels-Adler reactions to give heterocyclic annelated pyridines
- Frissen, August E.,Marcelis, Antonius T. M.,Plas, Henk C. van der
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p. 1589 - 1592
(2007/10/02)
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- FURTHER INTRAMOLECULAR DIELS-ALDER REACTIONS OF 1,2,4-TRIAZINES. SYNTHESIS OF DIHYDROPYRROLOpyridines
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3-(3-Butynylamino)-1,2,4-triazines undergo intramolecular Diels-Alder reactions to yield 2,3-dihydropyrrolopyridines
- Taylor, Edward C.,Pont, Joseph L.
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p. 379 - 382
(2007/10/02)
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