- Difluorocarbene-triggered cyclization: Synthesis of (hetero)arene-fused 2,2-difluoro-2,3-dihydrothiophenes
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An efficient method for the synthesis of (hetero)arene-fused 2,2-difluoro-2,3-dihydrothiophene derivatives using readily available sodium chlorodifluoroacetate (ClCF2CO2Na) has been developed. This transformation is achieved through a combination of a thi
- Liang, Huamin,Liu, Ran,Zhou, Min,Fu, Yue,Ni, Chuanfa,Hu, Jinbo
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supporting information
p. 7047 - 7051
(2020/09/15)
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- Formation of Aryl [1-Cyano-4-(dialkylamino)butadienyl] Ketones from Pyridines
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Treatment of 2-chloropyridine with LDA and the Weinreb amide of benzoic acid afforded three unusual products, namely N -methylbenzamide, 2-chloropyridine-3-methanol, and the ring-opened addition product. This same final product could also be obtained from 2-chloro-3-benzoylpyridine on treatment with LDA. Mechanistic insight for the formation of these products is provided.
- Gim, Hyo Jin,Jung, Michael E.
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p. 2548 - 2552
(2019/06/08)
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- COMPOUNDS AND METHODS FOR HEMATOPOIETIC REGENERATION
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The invention relates to compounds that promote hematopoietic regeneration. The invention further relates to methods of promoting hematopoietic regeneration using the novel compounds of the invention.
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Page/Page column 68; 69
(2019/06/17)
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- Aza-spirofluorene anthracene heterocyclic compound and application thereof in organic electroluminescence elements
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The invention relates to an aza-spirofluorene anthracene heterocyclic compound and an application thereof in organic electroluminescence elements. The aza-spirofluorene anthracene heterocyclic compound is represented by a general formula (1) (shown in the description), wherein groups of furan, carbazole, thiophene, fluorine, heteraryl amino, acridine, phenazine and the like are linked to a matrixof the compound. According to the aza-spirofluorene anthracene heterocyclic compound, the transmission property of a current carrier can be improved, the triplet state energy of a material can be improved, the HOMO/LUMO value of the material can be optimized, the high brightness, low voltage, high efficiency and long service life of an organic EL element can be realized, meanwhile, the material prepared from the compound has relatively high heat stability, the luminescence stability of a light emitting device can be remarkably improved, and the compound can be widely used as a luminescent layer main body material for OLED light emitting devices and display devices.
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Paragraph 0098; 0099; 0100
(2019/01/08)
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- Azine and Diazine Functionalization Using 2,2,6,6-Tetramethylpiperidino-Based Lithium-Metal Combinations: Application to the Synthesis of 5,9-Disubstituted Pyrido[3′,2′:4,5]pyrrolo[1,2- c ]pyrimidines
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The synthesis of triaryl methanols was investigated by reacting different 4-metalated 2-substituted pyrimidines with diaryl ketones, the latter being generated by deprotocupration-aroylation of azine and diazine substrates. Cyclization of the triaryl meth
- Marquise, Nada,Nguyen, Tan Tai,Chevallier, Floris,Picot, Laurent,Thiéry, Valérie,Lozach, Olivier,Bach, Stéphane,Ruchaud, Sandrine,Mongin, Florence
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supporting information
p. 2811 - 2816
(2015/12/18)
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- Efficient two-step access to azafluorenones and related compounds
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Crystals of a lithiocuprate prepared from copper(I) chloride and lithium 2,2,6,6-tetramethylpiperidide (2 equiv) were isolated and analyzed by X-ray diffraction as (TMP)2Cu(Cl)Li2·THF. The observation of this species is consistent with its having a role in deprotocupration- aroylation. Phenyl pyridyl ketones, phenyl quinolyl ketones, and phenyl thienyl ketones were prepared in tetrahydrofuran using the lithiocuprate and aroyl chorides as electrophiles. Diaryl ketones bearing a chloro group at the 2 position (of a pyridyl or phenyl group) thus synthesized were next converted through palladium-catalyzed ring closure to polycycles of the 5H-indeno[1,2-b]pyridin-5-one, 11H-indeno[1,2-b]quinolin-11-one, 9H-indeno[2,1-c]pyridin-9-one, and 8H-indeno[2,1-b]thiophen-8-one families.
- Marquise, Nada,Harford, Philip J.,Chevallier, Floris,Roisnel, Thierry,Wheatley, Andrew E.H.,Gros, Philippe C.,Mongin, Florence
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p. 3154 - 3157
(2013/06/27)
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- Synthesis of azafluorenones and related compounds using deprotocupration-aroylation followed by intramolecular direct arylation
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The efficiency of the deprotocupration-aroylation of 2-chloropyridine using lithiocuprates prepared from CuX (X=Cl, Br) and LiTMP (TMP=2,2,6,6- tetramethylpiperidido, 2 equiv) was investigated. CuCl was identified as a more suitable copper source than CuBr for this purpose. Different diaryl ketones bearing a halogen at the 2 position of one of the aryl groups were synthesized in this way from azines and thiophenes. These were then involved in palladium-catalyzed ring closure: substrates underwent expected CH-activation-type arylation to afford fluorenone-type compounds, and were also subjected to cyclization reactions leading to xanthones, notably in the presence of oxygen-containing substituents or reagents.
- Marquise, Nada,Harford, Philip J.,Chevallier, Floris,Roisnel, Thierry,Dorcet, Vincent,Gagez, Anne-Laure,Sablé, Sophie,Picot, Laurent,Thiéry, Valérie,Wheatley, Andrew E.H.,Gros, Philippe C.,Mongin, Florence
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p. 10123 - 10133
(2013/11/06)
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- Synthesis of 3-arylthieno[2,3-b]-, -[2,3-c]- or -[3,2-c]pyridines utilizing an interrupted pummerer reaction
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An efficient procedure for the synthesis of three types of thienopyridines has been developed. Thus, 3-(1-arylethenyl)-2-(ethylsulfinyl)pyridines, 4-(1-arylethenyl)-3-(ethylsulfinyl)pyridines, and 3-(1-arylethenyl)-4- (ethylsulfinyl)pyridines, which can be easily prepared from the respective aryl chloropyridinyl ketones in a three-step sequence, undergo an interrupted Pummerer reaction on treatment with excess acetic anhydride at temperatures ranging from 100 to 130 C to give 3-arylthieno[2,3-b]pyridines, 3-aryl-thieno[2,3-c]pyridines, and 3-arylthieno[3,2-c]pyridines, respectively. Georg Thieme Verlag Stuttgart - New York.
- Kobayashi, Kazuhiro,Suzuki, Teruhiko,Horiuchi, Mai,Shiroyama, Yasuhiko,Konishi, Hisatoshi
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experimental part
p. 2897 - 2906
(2011/10/18)
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- Deprotonative metalation of aromatic compounds by using an amino-based lithium cuprate
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Deprotonative cupration of aromatic compounds by using amino-based lithium cuprates was optimized with 2,4-dimethoxypyrimidine and 2-methoxypyridine as the substrates and benzoyl chloride as the electrophile. [(tmp)2CuLi] (+2 LiCl) (tmp=2,2,6,6-tetramethylpiperidino) was identified as the best reagent and its use was extended to anisole, 1,4-dimethoxybenzene, other substituted pyridines, furan, thiophene and derivatives, and N-Boc-indole (Boc=tert-butyloxycarbonyl). Of the electrophiles employed to attempt the interception of the generated aryl cuprates, aroyl chlorides, iodomethane, and diphenyl disulfide efficiently reacted. In addition, different oxidative agents were identified to afford symmetrical biaryls. Finally, palladium-catalyzed coupling with aryl halides was optimized and allowed the synthesis of different aryl derivatives in medium to good yields.
- Nguyen, Tan Tai,Marquise, Nada,Chevallier, Floris,Mongin, Florence
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experimental part
p. 10405 - 10416
(2011/10/12)
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- Deprotonative metalation of chloro- and bromopyridines using amido-based bimetallic species and regioselectivity-computed CH acidity relationships
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A series of chloro- and bromopyridines have been deprotometalated by using a range of 2,2,6,6-tetramethylpiperidino-based mixed lithium-metal combinations. Whereas lithium-zinc and lithium-cadmium bases afforded different mono- and diiodides after subsequent interception with iodine, complete regioselectivities were observed with the corresponding lithium-copper combination, as demonstrated by subsequent trapping with benzoyl chlorides. The obtained selectivities have been discussed in light of the CH acidities of the substrates, determined both in the gas phase and as a solution in THF by using the DFT B3LYP method.
- Snegaroff, Katia,Nguyen, Tan Tai,Marquise, Nada,Halauko, Yury S.,Harford, Philip J.,Roisnel, Thierry,Matulis, Vadim E.,Ivashkevich, Oleg A.,Chevallier, Floris,Wheatley, Andrew E. H.,Gros, Philippe C.,Mongin, Florence
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scheme or table
p. 13284 - 13297
(2012/02/03)
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- New Gilman-type lithium cuprate from a copper(II) salt: synthesis and deprotonative cupration of aromatics
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Deprotonative cupration of aromatics including heterocycles (anisole, 1,4-dimethoxybenzene, thiophene, furan, 2-fluoropyridine, 2-chloropyridine, 2-bromopyridine, and 2,4-dimethoxypyrimidine) was realized in tetrahydrofuran at room temperature using the Gilman-type amido-cuprate (TMP)2CuLi in situ prepared from CuCl2·TMEDA through successive addition of 1 equiv of butyllithium and 2 equiv of LiTMP. The intermediate lithium (hetero)arylcuprates were evidenced by trapping with iodine, allyl bromide, methyl iodide, and benzoyl chlorides, the latter giving the best results. Symmetrical dimers were also prepared from lithium azine and diazine cuprates using nitrobenzene as an oxidative agent.
- Nguyen, Tan Tai,Chevallier, Floris,Jouikov, Viatcheslav,Mongin, Florence
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experimental part
p. 6787 - 6790
(2010/04/29)
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- Synthetic studies on selective type 4 phosphodiesterase (PDE 4) inhibitors. 1. Structure-activity relationships and pharmacological evaluation of 1,8-naphthyridin-2(1H)-one derivatives.
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In order to develop novel and orally active phosphodiesterase (PDE) 4 inhibitors, random screening was performed using our chemical library to find YM-10335 possessing the 1,8-naphthyridin-2(1H)-one skeleton which is a completely different structure from rolipram. In this report, the syntheses and structure-activity relationships of the YM-10335 derivatives were described. Some compounds showed selective inhibitory activities for PDE 4 derived from human peripheral blood cells and no effect on the other PDE types (1, 2, 3, 5). The inhibition of the tumor necrosis factor-alpha (TNF-alpha) release in vitro and the carrageenan-induced pleurisy in rats were also described.
- Takayama, Kazuhisa,Iwata, Masahiro,Hisamichi, Hiroyuki,Okamoto, Yoshinori,Aoki, Motonori,Niwa, Akira
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p. 1050 - 1059
(2007/10/03)
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- 2-(Dimethylaminomethyl)-tetrahydroisoxazolopyridobenzazepine derivatives. Synthesis of a new 5-HT(2C) antagonist with potential anxiolytic properties.
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Following the program started at Johnson & Johnson Pharmaceutical Research & Development searching for 5-HT(2A/2C) antagonists, we now report on the synthesis of 2-(dimethylaminomethyl)-2,3,3a,8-tetrahydroisoxazolo[3,2-a]pyrido[3,4-c]-[2]benzazepine and 2-(dimethylaminomethyl)-2,3,3a,8-tetrahydroisoxazolo[3,2-a]pyrido[3,2-c]-[2]benzazepine. A new method for the synthesis of pyridobenzazepines is described as well. The affinities for several receptors as well as the mCPP antagonistic activity of the compounds synthesised are described.
- Andres, J Ignacio,Alonso, Jose M,Fernandez, Javier,Iturrino, Laura,Martinez, Pedro,Meert, Theo F,Sipido, Victor K
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p. 3573 - 3577
(2007/10/03)
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- Utilizing Acetyl Hypofluorite for Chlorination, Bromination, and Etherification of the Pyridine System
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Acetyl hypofluorite, which is easily made from F2, possesses a strong electrophilic fluorine.This electrophile is able to attach itself to the nitrogen atom of pyridine and activate the ring toward nucleophilic attacks.The ultimate elimination of HF results in an overall easy nucleophilic displacement of the hydrogen of the important 2-position .The nucleophiles used: Clδ-, Brδ-, ROδ-, originate from solvents such as CH2Cl2, CH2Br2, and various primary alcohols.Thus, 2-halo- or 2-alkoxypyridines were formed.The reaction conditions (room temperature, very short reaction times, and good yields) transform the task of direct substitution of the pyridine ring from an extremely difficult to a very easy procedure.
- Hebel, David,Rozen, Shlomo
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p. 6298 - 6301
(2007/10/02)
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- Improved Synthesis of 2,3-Disubstituted Pyridines by Metallation of 2-Chloropyridine: a Convenient Route to Fused Polyheterocycles
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Chemoselective directed metallation of 2-chloropyridine allows the synthesis of 2-substituted 3-carbonylated pyridines, advantage being taken of the metallation ortho-directing effect of the halogen, as well as its reactivity towards nucleophiles.Thus (2-chloro-, 2-methoxy-, and 2-amino-3-pyridyl)-ethanones and -arylmethanones as well as carbaldehydes have been prepared.Some of these ortho-disubstituted intermediates have been readily cyclized to fused polyheterocycles such as naphthiridines and aza-analoges of coumarins, xanthones, and acridones.
- Trecourt, Francois,Marsais, Francis,Guengoer, Timur,Queguiner, Guy
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p. 2409 - 2415
(2007/10/02)
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- Chlorination, Bromination, and Oxygenation of the Pyridine Ring Using AcOF Made from F2
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Acetyl hypofluorite reacts with pyridines in halogenated solvents or alcohols to give the corresponding 2-halo- or 2-alkoxypyridines.
- Hebel, David,Rozen, Shlomo
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p. 1123 - 1125
(2007/10/02)
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