582 results on '"Ring Closure"'
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302. Benzoxetes and Benzothietes ¾ Heterocyclic Analogues of Benzocyclobutene
- Author
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Herbert Meier
- Subjects
Double bond ,flash-vacuum-pyrolysis ,Pharmaceutical Science ,Review ,ring closure ,Analytical Chemistry ,lcsh:QD241-441 ,chemistry.chemical_compound ,lcsh:Organic chemistry ,Benzocyclobutene ,Computational chemistry ,Heterocyclic Compounds ,Drug Discovery ,Organic chemistry ,Polycyclic Compounds ,Physical and Theoretical Chemistry ,ring opening ,cycloaddition ,chemistry.chemical_classification ,Thermal equilibrium ,Valence (chemistry) ,photochemistry ,Flash vacuum pyrolysis ,Organic Chemistry ,Cycloaddition ,chemistry ,Chemistry (miscellaneous) ,Molecular Medicine ,Isomerization - Abstract
Benzo-condensed four-ring heterocycles, such as benzoxetes 1 and benzothietes 3 represent multi-purpose starting compounds for the preparation of various higher heterocyclic ring systems. The thermal or photochemical valence isomerizations between the benzenoid forms 1,3 and the higher reactive o-quinoid structures 2,4 provide the basis for the synthetic applications. On the other hand, this valence isomerization impedes in particular the generation and storage of 1 because the thermal equilibrium 1 ⇆ 2 is completely on the side of 2. Thus, the number of erroneous or questionable benzoxete structures published to date is surprisingly high. On the contrary, the thermal equilibrium 3 ⇆ 4 is on the side of the benzothietes 3, which makes them easily accessible, especially by different flash vacuum pyrolysis techniques. The present article gives a survey of the preparations of 1 and 2, and tries to stimulate their use in synthetic projects. Naphtho-condensed and higher condensed compounds and compounds with an exocyclic C=O or S=O double bond (lactones, thiolactones, sulfoxides and sulfones) are not covered in this article.
- Published
- 2012
303. Synthesis of Carbolines by Photostimulated Cyclization of Anilinohalopyridines
- Author
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Roberto A. Rossi, Gregory D. Cuny, Joydev K. Laha, and Silvia M. Barolo
- Subjects
Aniline Compounds ,Photolysis ,Radical-nucleophilic aromatic substitution ,Molecular Structure ,Photochemistry ,Chemistry ,Otras Ciencias Químicas ,Organic Chemistry ,Ciencias Químicas ,Catalysis ,purl.org/becyt/ford/1 [https] ,Srn1 ,Cyclization ,Ring Closure ,purl.org/becyt/ford/1.4 [https] ,Structural isomer ,Organic chemistry ,CIENCIAS NATURALES Y EXACTAS ,Palladium ,Carbolines - Abstract
A general synthetic route to prepare all four carboline regioisomers by photostimulated cyclization of anilinohalopyridines is described. The methodology affords various substituted carbolines in good to excellent yields. In the case of α-carbolines, the S(RN)1 methodology complements previously reported palladium-catalyzed cyclization approaches. Fil: Laha, Joydev K.. Harvard Medical School; Estados Unidos Fil: Barolo, Silvia Maricel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Rossi, Roberto Arturo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Cuny, Gregory D.. Harvard Medical School; Estados Unidos
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- 2011
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304. Palladium-Catalyzed Construction of Polycyclic Heterocycles by an Alkyne Insertion and Direct Arylation Cascade
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Hiroaki Ohno, Mutsumi Iuchi, Mio Yamamoto, Nobutaka Fujii, and Tetsuaki Tanaka
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chemistry.chemical_classification ,polycycles ,Aryl ,Organic Chemistry ,chemistry.chemical_element ,Alkyne ,ring closure ,Ring (chemistry) ,palladium ,Combinatorial chemistry ,Catalysis ,fused-ring systems ,chemistry.chemical_compound ,Cascade reaction ,chemistry ,Furan ,Thiophene ,tandem reaction ,Pyrrole ,Palladium - Abstract
Cascade cyclization of bromoenynes bearing an aryl group with catalytic amounts of palladium(II) acetate and cesium carbonate led to the direct construction of tri- or tetracyclic heterocycles. Direct arylation of a pyrrole, furan or thiophene ring in the cascade reaction affords the corresponding fused heteroarenes in moderate to good yields.
- Published
- 2011
305. TECHNIQUES D'ASSEMBLAGE D'ISOINDOLINONES STRUCTURELLEMENT AMENAGEES.APPLICATIONS ET DEVELOPPEMENTS
- Author
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Pierre Grandclaudon and Axel Couture
- Subjects
Alkaloids ,phthalimidines ,Lactams ,isoindolinones ,natural products ,bicyclic compounds ,Parham protocol ,lcsh:TP1-1185 ,ring closure ,lcsh:Chemical technology - Abstract
A number of conceptually new synthetic approaches to the elaboration of constitutionally diverse isoindolinones have been disclosed. The main objective was to develop synthetic tactics for the creation of the lactam unit that would allow for incorporation of appropriate functionalities liable to give access to an array of synthetic, natural and/or bioactive compounds through rather simple chemical manipulation. The flexibility and potentiality of these new processes have been further exemplified by the total synthesis of exemplary representatives in both series, i.e. alkaloids and compounds endowed with chemotherapeutic properties.
- Published
- 2010
306. Synthesis of Carbazoles by Intramolecular Arylation of Diarylamide Anions
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Sandra E. Martin, María E. Budén, Victoria A. Vaillard, and Roberto A. Rossi
- Subjects
Intramolecular reaction ,Carbazoles ,Medicinal chemistry ,Chemical synthesis ,CARBAZOLES ,Catalysis ,chemistry.chemical_compound ,Benzene Derivatives ,RING CLOSURE ,Organic chemistry ,ELECTRON TRANSFER ,Azepine ,Substitution reaction ,Aniline Compounds ,Radical-nucleophilic aromatic substitution ,Benzidines ,Otras Ciencias Químicas ,Aryl ,Organic Chemistry ,Ciencias Químicas ,Photochemical Processes ,Amides ,Kinetics ,SRN1 ,chemistry ,Intramolecular force ,CIENCIAS NATURALES Y EXACTAS - Abstract
The synthesis of a series of substituted 9H-carbazoles by the photostimulated SRN1 substitution reactionwith diarylamines as starting substrate was performed. The diarylamines were obtained by two approaches,the Pd-catalyzed reactions (Buchwald-Hartwig) or Cu-catalyzed reactions of 2-haloanilines with aryl halides, or 2-bromoiodobenzene with anilines, with moderate to very good isolated yields (45-89%).Through an intramolecular C-C bond formation of diarylamines by the SRN1 mechanism, Carbazoles were achieved. These reactions proceeded synthetically in very good to excellent yields (81-99%) in liquid ammonia and DMSO. The reaction of N-(2-bromophenyl)-2-phenylbenzenamine gave 1-phenyl-9H-carbazole (38%) and the isomer 9H-tribenz[b,d,f]azepine (58%). By using this methodology, 9Hcarbazoles, substituted 9H-carbazoles, benzocarbazoles, and even 3,3′-bi(9H-carbazole) were obtained by a double SRN1 reaction with benzidine. Fil: Buden, Maria Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Vaillard, Victoria Anahi. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina Fil: Martín, Sandra Elizabeth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Rossi, Roberto Arturo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
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- 2009
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307. A new synthesis of the s-triazolo[1,5- a]pyridine ring system.
- Author
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Hajós, G., Timári, G., Messmer, A., Zagyva, A., Miskolczi, I., and Schantl, J.
- Abstract
Copyright of Chemical Monthly / Monatshefte für Chemie is the property of Springer Nature and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
- Published
- 1995
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308. Multi‐Gram Scale Synthesis of Chiral 3‐Methyl‐2,5‐trans‐tetrahydrofurans.
- Author
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Qin, Shuanglin, Cao, Yuting, Luo, Yunhao, Jiang, Shende, Clark, J. Stephen, Wang, Xiaoji, and Yang, Guang
- Subjects
- *
CHEMICAL yield , *HYDROLYSIS - Abstract
In this article, we report the rapid and facile synthesis of chiral 3‐methyl‐2,5‐trans‐tetrahydrofurans. This reaction utilizes cheap and easily available starting materials. A domino hydrolysis and intramolecular Michael‐type ring closure reaction was the key step. As a result, synthesis of the desired 3‐methyl‐2,5‐trans‐tetrahydrofurans could be achieved in gram‐scale over seven linear steps with high chemical yield and high diastereoselectivity. [ABSTRACT FROM AUTHOR]
- Published
- 2019
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309. Front Cover: Real‐Time Observation of Diarylethene‐Based Photoswitches in a Cyclic Peptide Environment (ChemPhotoChem 6/2019).
- Author
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Schweigert, Caroline, Babii, Oleg, Afonin, Sergii, Schober, Tim, Leier, Julia, Michenfelder, Nadine C., Komarov, Igor V., Ulrich, Anne S., and Unterreiner, Andreas Neil
- Subjects
- *
CYCLIC peptides , *PEPTIDOMIMETICS - Published
- 2019
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310. Novel aluminium compounds derived from Schiff bases: Synthesis, characterization and catalytic performance in hydroboration.
- Author
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Jin, Da, Ma, Xiaoli, Liu, Yashuai, Peng, Jiong, and Yang, Zhi
- Subjects
- *
COMPLEX compounds synthesis , *ALUMINUM compounds , *SCHIFF bases , *HYDROBORATION , *METAL complexes , *LIGANDS (Chemistry) , *CATALYTIC activity - Abstract
Seven novel aluminium complexes supported by Schiff base ligands derived from o‐diaminobenzene or o‐aminothiophenol were synthesized and characterized. The reactions of AlMe3 with L1 (N,N′‐bis(benzylidine)‐o‐phenylenediamine) and L2 (N,N′‐bis(2‐thienylmethylene)‐o‐phenylenediamine) gave the complexes L1AlMe3 (1) and L2AlMe2 (2), respectively, which involved two types of reaction mechanisms: one was proton transfer and ring closure, and the other was alkyl transfer. Complexes L3AlMe2 (HL3 = 4‐chlorobenzylidene‐o‐aminothiophenol) (3), L4AlMe2 (HL4 = 2‐thiophenecarboxaldehyde‐o‐aminothiophenol) (4), L3AlH(NMe3) (5), L4AlH(NMe3) (6) and L5AlH(NMe3) (HL5 = 4‐methylbenzylidene‐o‐aminothiophenol) (7) were prepared by reacting HL3–5 with equimolar AlMe3 or H3Al⋅NMe3, respectively. Compounds 3–7 feature an organic–inorganic hybrid containing CNAlSC five‐membered ring. All complexes were characterized using 1H NMR and 13C NMR spectroscopy, X‐ray crystal structure analysis and elemental analysis. The efficient catalytic performances of 1–7 for the hydroboration of carbonyl groups were investigated, with compound 4 exhibiting the highest catalytic activity among all the complexes. Seven novel aluminium complexes were synthesized and fully characterized. All of them displayed excellent catalytic activity in hydroboration reactions. [ABSTRACT FROM AUTHOR]
- Published
- 2019
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311. Rh(I)-Catalyzed Cycloisomerization of 1,6-Enynes
- Author
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Jonathan A. Ellman, Robert G. Bergman, Eric M. Phillips, and Yuji Matsushima
- Subjects
chemistry.chemical_classification ,Reaction mechanism ,Chemistry ,Organic Chemistry ,Alkyne ,chemistry.chemical_element ,Homogeneous catalysis ,ring closure ,enones ,homogeneous catalysis ,Medicinal chemistry ,isomerization ,Article ,Catalysis ,Rhodium ,Medicinal and Biomolecular Chemistry ,chemistry.chemical_compound ,Cycloisomerization ,rhodium ,Organic chemistry ,Isomerization ,Derivative (chemistry) - Abstract
A new and unexpected Rh(I)-catalyzed cycloisomerization of 1,6-enynes is reported. Several different alkyne substitution patterns were evaluated under the reaction conditions, including a deuterated derivative that provides some insight into the reaction mechanism.
- Published
- 2015
312. Novel stereocontrolled syntheses of tashiromine and epitashiromine
- Author
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Loránd Kiss, Enikő Forró, and Ferenc Fülöp
- Subjects
chemistry.chemical_classification ,amino acids ,Double bond ,Bicyclic molecule ,Chemistry ,Stereochemistry ,Organic Chemistry ,stereocontrolled synthesis ,ring closure ,Ring (chemistry) ,alkaloids ,Combinatorial chemistry ,Full Research Paper ,lcsh:QD241-441 ,chemistry.chemical_compound ,lcsh:Organic chemistry ,Cyclooctene ,lcsh:Q ,lcsh:Science ,ring opening ,Tashiromine - Abstract
A novel stereocontrolled approach has been developed for the syntheses of tashiromine and epitashiromine alkaloids from cyclooctene β-amino acids. The synthetic concept is based on the azetidinone opening of a bicyclic β-lactam, followed by oxidative ring opening through ring C–C double bond and reductive ring-closure reactions of the cis- or trans-cyclooctene β-amino acids.
- Published
- 2015
313. Short Synthesis of (R)- and (S)-4-Amino-3-Hydroxybutyric Acid (GABOB)
- Author
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Luana Bagnoli, Raffaella Terlizzi, Lorenzo Testaferri, Francesca Marini, Marcello Tiecco, Claudio Santi, and Andrea Temperini
- Subjects
chemistry.chemical_classification ,amino acids ,Stereochemistry ,Organic Chemistry ,selenium oxidation ,ring closure ,beta-hydroxyselenides ,1 ,3-oxazolin-2-ones ,Alcohol ,General Medicine ,Catalysis ,Amino acid ,chemistry.chemical_compound ,Stereospecificity ,chemistry ,Organic chemistry ,3-Hydroxybutyric Acid - Abstract
A simple and stereospecific synthesis of both (R)- and (S)-GABOB has been developed. The synthetic approach involves the conversion, through organoselenium intermediates, of commercially available ethyl (R)- and (S)-4-chloro-3-hydroxybutyrate into a protected 1,2-amino alcohol with retention of the original configuration.
- Published
- 2005
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314. Oxidative cleavage of a cyclic hemiketal in the presence of copper(II) and structural characterization of the product complex
- Author
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Marjani, Katayoun, Asgarian, Jafar, and Mousavi, Mohsen
- Published
- 2008
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315. Synthesis of derivatives of the new heterocyclic system pyrimido[5′,4′:5,6]pyrido[3,2-b]indole
- Author
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Ryabova, S. Yu., Alekseeva, L. M., Masterova, N. S., and Granik, V. G.
- Published
- 2007
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316. A Novel Route to 1,2,3-Thiadiazole, 1,3,4-Thiadiazine, and 1,2,5-Triazepine Derivatives
- Author
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Barbara Zaleska, Paweł Serda, Jacek Grochowski, and Bartosz Trzewik
- Subjects
heterocycles ,thiadiazine ,Chemistry ,cyclizations ,Organic Chemistry ,Organic chemistry ,thiadiazole ,Reactivity (chemistry) ,General Medicine ,ring closure ,triazepine ,Combinatorial chemistry ,Catalysis - Abstract
New convenient methods for the synthesis of 1,2,3-thiadiazole, 1,3,4-thiadiazine, and 1,2,5-triazepine derivatives are reported. In the heterocyclization process, the reactivity of 1-thia-4-aza-1,3-butadiene system of syn-2-phenylhydrazono-3-oxothiobutanoic acid anilides was exploited.
- Published
- 2003
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317. A radical route in the biomimetic oxidation of a tertiary amine
- Author
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Patrizia Gentili, Andrea Cuppoletti, Carlo Galli, and Horia Petride
- Subjects
Steric effects ,hydrogen abstraction ,oxidation: hydrogen abstraction ,Tertiary amine ,oxidation ,Chemistry ,Organic Chemistry ,Imine ,ring closure ,aziridines ,flash photolysis ,Aziridine ,Photochemistry ,Medicinal chemistry ,Electron transfer ,chemistry.chemical_compound ,Cobalt-mediated radical polymerization ,Tetraphenylporphyrin ,Flash photolysis ,Physical and Theoretical Chemistry - Abstract
Whereas the biomimetic oxidative N-dealkylation of tertiary amines with t-BuOOH and an iron(III) tetraphenylporphyrin typically proceeds by an electron transfer (ET) route, a radical H-atom transfer (HAT) route has been found to operate with N-benzylaziridine (1), an amine that is fairly resistant towards one-electron oxidation for steric reasons. New mechanistic information is presented in favour of this radical route, and the exclusive formation of the dimeric product N,N′-dibenzylpiperazine (2) is explained in the light of the Baldwin's rules. Flash photolysis data provide a rate constant of 1.7 × 105 s−1 for the ring opening of the aziridine radical (1.) to the imine radical (4.) in the early stages of the process leading to 2. Semiempirical calculations indicate the ring-opened radical 4. to be more stable than 1.. Copyright © 2002 John Wiley & Sons, Ltd.
- Published
- 2002
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318. Preparation of Substituted Methyl o-Nitrophenyl Sulfides
- Author
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Frantisek Castek, Katerina Dudova, Petr Simunek, and Vladimír Macháček
- Subjects
Base (chemistry) ,Pharmaceutical Science ,ring closure ,Ring (chemistry) ,Medicinal chemistry ,Article ,Analytical Chemistry ,lcsh:QD241-441 ,chemistry.chemical_compound ,lcsh:Organic chemistry ,Nucleophilic aromatic substitution ,Drug Discovery ,Pyridine ,Nucleophilic substitution ,Organic chemistry ,Physical and Theoretical Chemistry ,Triethylamine ,Carbanion ,sulfur nucleophiles ,chemistry.chemical_classification ,Organic Chemistry ,chemistry ,Chemistry (miscellaneous) ,Nitro ,Molecular Medicine - Abstract
The nucleophilic substitution of substituted o-nitrochlorobenzenes with substituted methanethiolates, catalysed with triethylamine or pyridine, has been used to prepare a series of appropriately substituted methyl-o-nitrophenylsulfides. The prepared compounds were identified by their 1H- and 13C-NMR spectra. The base catalysed ring closure of methyl 2-(methoxycarbonylmethylsulfanyl)-3,5-dinitrobenzenecarboxylate only results in an attack of carbanion on the ester group, not on a nitro group as with the other compounds prepared. The cyclisation product is methyl 3-hydroxy-5,7-dinitro-benzo[b]thiophene-2-carboxylate (11).
- Published
- 2002
319. New methodology for the synthesis of benzoazacrown ethers by transformation of the macrocycle of benzocrown ethers
- Author
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Gromov, S. P., Dmitrieva, S. N., Vedernikov, A. I., and Churakova, M. V.
- Published
- 2004
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320. Synthesis of Substituted 2-Benzoylaminothiobenzamides and Their Ring Closure to Substituted 2-Phenylquinazoline-4-thiones
- Author
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Jiří Hanusek, Miloš Sedlák, Ludmila Hejtmánková, and Lenka Kubicová
- Subjects
2-Benzoylaminothiobenzamides ,quinazoline-4-thiones ,tautomerism ,ring closure ,Sodium ,Substituent ,Pharmaceutical Science ,chemistry.chemical_element ,Ring (chemistry) ,Medicinal chemistry ,Article ,Analytical Chemistry ,lcsh:QD241-441 ,Acylation ,chemistry.chemical_compound ,symbols.namesake ,lcsh:Organic chemistry ,Drug Discovery ,Atom ,Organic chemistry ,Physical and Theoretical Chemistry ,Organic Chemistry ,Tautomer ,Sulfur ,chemistry ,Chemistry (miscellaneous) ,symbols ,Molecular Medicine ,Raman spectroscopy - Abstract
Acylation of 2-aminothiobenzamide or 2-methylaminothiobenzamide with substituted benzoyl chlorides has been used to synthesise the corresponding 2-benzoyl-aminothiobenzamides whose subsequent sodium methoxide-catalysed ring closure gives the corresponding quinazoline-4-thiones. These compounds were characterised by means of their 1H- and 13C-NMR spectra. The preferred tautomeric form of selected compounds has been discussed on the basis of their 13C-NMR, IR and Raman spectra. It has been found that in the given medium 1-methyl-quinazoline-4-thiones undergo a replacement of the sulphur substituent by oxygen giving 1-methyl-quinazoline-4-ones. In strong acid media, 2-benzoylaminothiobenzamide is cyclised through its sulphur atom to give 2-phenylbenzo[d-1,3]thiazin-4-one.
- Published
- 2001
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321. Rh(I)-Catalyzed Cycloisomerization of 1,6-Enynes.
- Author
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Matsushima, Yuji, Matsushima, Yuji, Phillips, Eric M, Bergman, Robert G, Ellman, Jonathan A, Matsushima, Yuji, Matsushima, Yuji, Phillips, Eric M, Bergman, Robert G, and Ellman, Jonathan A
- Abstract
A new and unexpected Rh(I)-catalyzed cycloisomerization of 1,6-enynes is reported. Several different alkyne substitution patterns were evaluated under the reaction conditions, including a deuterated derivative that provides some insight into the reaction mechanism.
- Published
- 2015
322. A facile synthesis of 1,3-disilacyclohexanes
- Author
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Naoko Inamasu, Katsuya Mizuno, Tamejiro Hiyama, Masaki Shimizu, and Hirokazu Masai
- Subjects
silacyclopropane ,ab initio calculation ,Dimethylsilane ,Silylation ,Cyclohexane ,polysilacycloalkanes ,Ab initio ,ring closure ,Ring (chemistry) ,Medicinal chemistry ,Inorganic Chemistry ,chemistry.chemical_compound ,chemistry ,Computational chemistry ,Electrophile ,Materials Chemistry ,Methyllithium ,Reactivity (chemistry) ,Physical and Theoretical Chemistry ,1,3-disilacyclohexanes - Abstract
Novel synthesis of 1,3-disilacyclohexanes is achieved by silylation of bis(alkylthio)methyllithium with chloro(chloromethyl)dimethylsilane followed by ring closure with a base. The spiro-fused disilacyclohexane ring is shown to be structurally strain-free, like cyclohexane. A reaction mechanism is proposed involving a silacyclopropane intermediate whose electrophilic reactivity at silicon is supported by ab initio calculation.
- Published
- 1999
323. Al/P- and Ga/P-Based Frustrated Lewis Pairs and Electronically Unsaturated Substrates: Ring Cleavage and Ring Closure, C-C and C-N Bond Formation.
- Author
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Pleschka D, Uebing M, Lange M, Hepp A, Wübker AL, Hansen MR, Würthwein EU, and Uhl W
- Abstract
Al/P- and Ga/P-based frustrated Lewis pairs (FLPs) reacted with an azirine under mild conditions under cleavage of the heterocycle on two different positions. Opening of the C-C bond yielded an unusual nitrile-ylide adduct in which a C-N moiety coordinated to the FLP backbone. Cleavage of a C-N bond afforded the thermodynamically favored enamine adduct with the N atom bound to P and Al or Ga atoms. Ring closure was observed upon treatment of an Al/P FLP with electronically unsaturated substrates (4-(1-cyclohexenyl)-1-aza-but-1-en-3-ynes) and yielded by C-N bond formation hexahydroquinoline derivatives, which coordinated to the FLP through P-C and Al-C bonds. Diphenylcyclopropenone showed a diverse reactivity, which depending on steric shielding and the polarizing effect of Al or Ga atoms afforded different products. An AltBu
2 /P FLP yielded an adduct with the C=O group coordinated to P and Al. The dineopentyl derivative gave an equilibrium mixture consisting of a similar product and a simple adduct with O bound to Al and a three-coordinate P atom. Both compounds co-crystallize. The Ga/P FLP only formed the simple adduct with the same substrate. Rearrangement resulted in all cases in C3 -ring cleavage and migration of a mesityl group from P to a former ring C atom by C-C bond formation. Diphenylthiocyclopropenone (evidence for the presence of P=C bonds) and an imine derivative afforded similar products., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)- Published
- 2019
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324. Strategies for the synthesis of cyclic ethers of marine natural products
- Author
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Víctor S. Martín, Juan I. Padrón, Tomás Martín, Ministerio de Economía y Competitividad (España), and European Commission
- Subjects
Trimethylsilyl ,010405 organic chemistry ,Chemistry ,Organic Chemistry ,Nicholas reaction ,Halide ,Total synthesis ,Heterocycles ,Prins reaction ,010402 general chemistry ,Metathesis ,01 natural sciences ,0104 chemical sciences ,chemistry.chemical_compound ,Cyclization ,Ring Closure ,Alkoxy group ,Total Synthesis ,Organic chemistry ,Natural Products ,Ethers - Abstract
This account describes our studies on the synthesis of natural products that contain cyclic ethers in their structures. An overview of the main methodologies is presented and several total syntheses developed by the group are described. We also discuss new applications based on the use of Prins and Nicolas reactions as key steps in the preparation of oxygenated heterocyclic compounds., This research was supported by the Spanish MINECO, co-financed by the European Regional Development Fund (ERDF) (CTQ2011- 28417-C02-01/BQU and CTQ2011-22653) and the IMBRAIN project (FP7-REGPOT-2012-CT2012-31637-IMBRAIN), which is funded under the Seventh Framework Programme (CAPACITIES).
- Published
- 2014
325. Alexander Valerianovich Butin (18.05.1962–1.05.2015)
- Author
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Rubtsov, A. E. and Trushkov, I. V.
- Published
- 2015
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326. Bazı kinoksalin türevlerinin sentezi
- Author
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Hepbay, Çiğdem, Karataş, İbrahim, Kimya Anabilim Dalı, and Enstitüler, Fen Bilimleri Enstitüsü, Kimya Ana Bilim Dalı
- Subjects
Halka kapanması ,Quinoxaline ,Cyclization reaction ,Kondensasyon reaksiyonu ,Kinoksalinler ,Ketoksimler ,Kimya ,Keto oximes ,Chemistry ,Ketoximes ,Quinoxalines ,"null" ,Condensation reaction ,Ring closure - Abstract
Bu çalışmada yeni kinoksalin türevlerinin sentezi tanımlanmıştı. İlk olarak, izonitrosoasetofenon, izonitroso-1-asetilnaftalin ve izonitroso-4-asetilbifenil bileşikleri, izopentil nitrit ile sırasıyla asetofenon, 1-asetilnaftalin ve 4-asetilbifenil bileşiklerinin reaksiyonundan elde edilmiştir. Daha sonra o-fenilendiamin türevleri ile elde edilen bu keto oksim bileşiklerinin kondensasyon reaksiyonlarından farklı kinoksalin türevleri sentezlenmiştir. Sentezlenen kinoksalin türevlerinin yapıları FT-IR, 1H-NMR ve 13C-NMR teknikleri kullanılarak aydınlatılmıştır., This study describes the synthesis of novel quinoxaline derivatives. Firstly, isonitrosoacetophenone, isonitroso-1-acetylnaphthalene and isonitroso-4-acetylbiphenyl were synthesized from the reaction of isopentylnitrite with acetophenone, 1-acetylnaphthalene and 4-acetylbiphenyl respectively. Then, derivatives of quinoxaline were prepared from the condensation reaction of keto oximes with derivatives of o-phenylenediamine. Structures of the obtained products were confirmed by FT-IR, 1H-NMR and 13C-NMR techniques., Bu tez çalışması BAP tarafından 11201002 nolu proje ile desteklenmiştir.
- Published
- 2013
327. Electron impact induced fragmentation of aromatic N-alkoxy-imines I. Ring closure in (M-CH2O)+• ions by intramolecular aromatic substitution
- Author
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Pongratz, H., Mayer, K. K., and Wiegrebe, W.
- Published
- 1997
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328. Alkynedicobalt Complexes in γ-Carbonyl Cations and Cycloheptynedicobalt Complexes
- Author
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James R. Green
- Subjects
Chemistry ,Stereochemistry ,Organic Chemistry ,Umpolung ,ring closure ,Carbocation ,Medicinal chemistry ,Cycloaddition ,Ion ,transition-metal ,Microstegiol ,carbocation ,Transition metal ,Intramolecular force ,Electrophile ,alkyne complexes ,Biochemistry, Biophysics, and Structural Biology - Abstract
This Account describes our work on highly electrophilic γ-carbonyl cations featuring propargyldicobalt cations, cycloheptynedicobalt complexes, and the interconnection between the two systems. 1 Introduction 2 γ-Carbonyl Cations via Iron Allyl Cations 3 γ-Carbonyl Cations via Propargyldicobalt Cations 3.1 Synthesis of Velloziolide 3.2 Synthesis of Microstegiol 4 Synthesis of Cycloheptynedicobalt Complexes 4.1 Synthesis via γ-Carbonyl Cations 4.2 Cycloheptynedicobalt Complexes via [4+3] Cycloaddition Reactions 4.3 Cycloheptynedicobalt Complexes via Ring-Closing Metathesis 4.4 Cycloaddition Reactions on Cycloheptynedicobalt Complexes 4.5 Cycloheptynedicobalt Complexes via Intramolecular Nicholas Reactions 5 Dehydrotropylium Ion Co2(CO)6 Complex 6 Final Comments
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- 2012
329. General synthetic approach to 2-phenolic adenine derivatives
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Carla Correia, M. Alice Carvalho, M. Fernanda R. P. Proença, Ashly Rocha, and Universidade do Minho
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Aldehydes ,Nucleobases ,Science & Technology ,010405 organic chemistry ,Chemistry ,Organic Chemistry ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,3. Good health ,Nucleobase ,chemistry.chemical_compound ,Condensations ,Phenols ,Simple (abstract algebra) ,Organic chemistry ,Ring closure ,Adenine derivatives - Abstract
A simple and general “one pot” procedure for the synthesis of 2,9-diarylpurines with one or multiple hydroxyl groups in the 2- aryl unit is described, from the reaction of 5-amino-4-amidinoimidazoles with phenolic aldehydes., National NMR Network, Fundação para a Ciência e a Tecnologia (FCT). F.C.T. (project nºF-COMP-01-0124-FEDER-022716 (ref. FCT PEst-/QUI/UI0686/2011) FEDER-COMPETE, FCT-Portugal and the PhD grant to C. Correia (SFRH/BD/22270/2005).
- Published
- 2012
330. Carboxylate-Directed Tandem Functionalizations of α,β-Dihaloalkenoic Acids with 1-Alkynes: A Straightforward Access to (Z)-Configured, α,β-Substituted γ-Alkylidenebutenolides
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Mohamed Abarbri, Jérôme Thibonnet, Jean-Luc Parrain, A. Duchene, Samuel Inack Ngi, Khalil Cherry, Laurent Commeiras, Virginie Héran, Laboratoire Physicochimie des matériaux et des biomolécules (PCMB - EA4244), Faculté des sciences et techniques de Tours, STeRéO, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), Université François Rabelais Département de Chimie, Laboratoire PCMB 32 Avenue Monge, 37200 Tours, and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
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Stereochemistry ,butyrolactones ,Carboxylic Acids ,chemistry.chemical_element ,ring closure ,010402 general chemistry ,01 natural sciences ,Catalysis ,chemistry.chemical_compound ,4-Butyrolactone ,Carboxylate ,heterocycles ,copper catalysis ,Tandem ,Molecular Structure ,010405 organic chemistry ,Chemistry ,Hydrocarbons, Halogenated ,[CHIM.ORGA]Chemical Sciences/Organic chemistry ,Organic Chemistry ,domino reactions ,Stereoisomerism ,General Chemistry ,Copper ,3. Good health ,0104 chemical sciences ,Alkynes - Abstract
International audience; An easy and mild copper(I)-catalysed lactonisation of readily available (E)-2,3-dihalopropenoic acid derivatives regio- and stereoselectively leads to rarely described (Z)-3-halo-5-ylidene-5H-furan-2-ones. These compounds are subsequently able to undergo classical Pd-catalysed cross-coupling reactions, providing 3-substituted and 3,4-disubstituted 5-ylidene-5H-furan-2-ones
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- 2011
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331. One-pot synthesis of new aza- and diaza-aminopenanthrenes
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Patrick Dallemagne, Thomas Cailly, Rodrigue Yougnia, Christophe Rochais, Jana Sopkova‐de Oliveira Santos, Sylvain Rault, Centre d'Etudes et de Recherche sur le Médicament de Normandie ( CERMN ), Université de Caen Normandie ( UNICAEN ), Normandie Université ( NU ) -Normandie Université ( NU ), Centre d'Etudes et de Recherche sur le Médicament de Normandie (CERMN), Université de Caen Normandie (UNICAEN), and Normandie Université (NU)-Normandie Université (NU)
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Phenanthroline ,Fused ring system ,One-pot synthesis ,[CHIM.THER]Chemical Sciences/Medicinal Chemistry ,Azaphenanthrene ,010402 general chemistry ,Ring (chemistry) ,Dieckmann–Thorpe ,01 natural sciences ,Biochemistry ,Chemical synthesis ,Benzoquinoline ,chemistry.chemical_compound ,Suzuki–Miyaura cross-coupling ,Drug Discovery ,Organic chemistry ,Ring closure ,ComputingMilieux_MISCELLANEOUS ,010405 organic chemistry ,Chemistry ,Organic Chemistry ,Quinoline ,[ CHIM.THER ] Chemical Sciences/Medicinal Chemistry ,Combinatorial chemistry ,0104 chemical sciences ,One pot reaction ,Microwave irradiation - Abstract
International audience; The synthesis of a series of benzo(iso)quinoline and phenanthroline derivatives has been achieved using an efficient one-pot procedure. It proceeds through a Suzuki–Miyaura cross-coupling followed by a Dieckmann–Thorpe ring closure under microwave irradiation and provides easy access to building blocks not readily available through other methods
- Published
- 2011
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332. Oxazole/Thiazole and Triazole Hybrids Based on ¿-Amino Acids
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Instituto de Salud Carlos III, European Commission, Consejo Superior de Investigaciones Científicas (España), Ministerio de Economía y Competitividad (España), Valdomir, Guillermo, Padrón, Juan I., Padrón, José M., Martín, Víctor S., Davyt, Danilo, Instituto de Salud Carlos III, European Commission, Consejo Superior de Investigaciones Científicas (España), Ministerio de Economía y Competitividad (España), Valdomir, Guillermo, Padrón, Juan I., Padrón, José M., Martín, Víctor S., and Davyt, Danilo
- Abstract
The Cu(I)-catalyzed Huisgen [3+2] cycloaddition is the basis of click chemistry to synthesize triazole derivatives by coupling azides with ethynyl blocks. In the development of new compounds inspired by bioactive natural products, the synthesis of new oxazole building blocks containing azide moiety and coupling them with aromatic alkynes via triazole linker is described. These oxazole building blocks are synthesized using amino acids as chiral and inexpensive starting materials. Using this approach, 16 new triazole-oxazole hybrids were synthesized.
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- 2014
333. Strategies for the synthesis of cyclic ethers of marine natural products
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Ministerio de Economía y Competitividad (España), European Commission, Martín, Tomás, Padrón, Juan I., Martín, Víctor S., Ministerio de Economía y Competitividad (España), European Commission, Martín, Tomás, Padrón, Juan I., and Martín, Víctor S.
- Abstract
This account describes our studies on the synthesis of natural products that contain cyclic ethers in their structures. An overview of the main methodologies is presented and several total syntheses developed by the group are described. We also discuss new applications based on the use of Prins and Nicolas reactions as key steps in the preparation of oxygenated heterocyclic compounds.
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- 2014
334. One-pot synthesis of novel poly-substituted phenanthrenes
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Jana Sopkova‐de Oliveira Santos, Patrick Dallemagne, Christophe Rochais, Sylvain Rault, Rodrigue Yougnia, Centre d'Etudes et de Recherche sur le Médicament de Normandie (CERMN), Université de Caen Normandie (UNICAEN), and Normandie Université (NU)-Normandie Université (NU)
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010405 organic chemistry ,[CHIM.ORGA]Chemical Sciences/Organic chemistry ,Fused ring system ,Organic Chemistry ,One-pot synthesis ,Phenanthrene ,010402 general chemistry ,Ring (chemistry) ,Dieckmann–Thorpe ,01 natural sciences ,Biochemistry ,Combinatorial chemistry ,Chemical synthesis ,Suzuki–Miyaura cross-couplin ,0104 chemical sciences ,chemistry.chemical_compound ,chemistry ,One pot reaction ,Drug Discovery ,Microwave irradiation ,Phenanthrenes ,Ring closure - Abstract
International audience; A one-pot synthesis of novel poly-substituted phenanthrenes is described in this article through a Suzuki–Miyaura cross-coupling followed by a Dieckmann–Thorpe ring closure under microwave irradiation. The selection of the appropriate starting materials allowed us to introduce diversity on various positions of the phenanthrene ring system
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- 2010
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335. Catalytic oxidation of N -phenylamidrazones to 1,3-Diphenyl-1,4-dihydro-1, 2,4-benzotriazin-4-yls: An improved synthesis of blatters radical
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Koutentis, Panayiotis Andreas, Lo Re, D., and Koutentis, Panayiotis Andreas [0000-0002-4652-7567]
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oxidation ,Heterocycles ,DBU ,Related derivatives ,Medicinal chemistry ,Catalysis ,1,3 diphenyl 1,4 dihydro 1,2,4 benzotriazin 4 yl ,alkene derivative ,Oxidations ,physical chemistry ,Ring closure ,Gram scale ,radical ,Benzotriazines ,n phenylamidrazone derivative ,Ring closures ,Chemistry ,carbon ,Organic Chemistry ,thin layer chromatography ,article ,Catalytic oxidation ,Reaction conditions ,unclassified drug ,reaction analysis ,Organic radicals ,1,8 diazabicyclo[5.4.0]undec 7 ene ,Synthesis (chemical) ,chemical modification ,Palladium - Abstract
Blatters radical, 1,3-diphenyl-1,4-dihydro-1,2,4-benzotriazin-4-yl (1a, R =H), and several of its C-7 substituted analogues (R =CF3, Cl, Br, I, Me, OMe) were prepared in good-to-excellent yields through catalytic oxidation of the corresponding amidrazones by using palladium-on-carbon (1.6 mol%) and 1,8-diazabicyclo[5.4.0]undec-7-ene (0.1-1.0 equiv) in air. The reaction conditions were suitable for the preparation of Blatters radical on a one-gram scale in up to 87% yield. © Georg Thieme Verlag Stuttgart. 12 2075 2079 Cited By :36
- Published
- 2010
336. Anions [N(CH 2) 3 and ON(CH 2) 2- Are stable in the gas phase, but can they be charge stripped to form the radicals N(CH 2) 3 and ON(CH 2) 2 A joint experimental and theoretical study
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Fitzgerald, M, Dua, Suresh, Bilusich, D, Eichinger, Peter Charles Hans, Peppe, Salvatore, and Bowie, John
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[N(CH2)3] ,[ON(CH2)2] ,neutralisation arrangement ,energised [N(CH2)3] and [ON(CH2)2] ,ring closure ,fragmentation - Abstract
Collision-induced activation of deprotonated trimethylamine N-oxide yields the two anions [N(CH(2))(3)](-) and [ON(CH(2))(2)](-) following losses of H(2)O and CH(4), respectively. These two anions decompose by minor losses of H(*) and H(2) when collisionally activated: no other fragmentations are noted. Calculations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31+G(d) level of theory indicate that these trigonal anions are stable, and should not rearrange following collisional activation. Collisional-induced charge stripping of the anions [N(CH(2))(3)](-) and [ON(CH(2))(2)](-), respectively, form N(CH(2))(3) and ON(CH(2))(2). Some of these neutrals are energised and undergo rearrangement and dissociation. From a consideration of experiment and theory, it is proposed (i) that energised N(CH(2))(3) may cyclise to form the 1-aziridinylcarbinyl radical. This species may ring open to CH(2)=NCH(2)CH(2) which then decomposes to CH(2)N and C(2)H(4) and (ii) energised ON(CH(2))(2) may undergo OC cyclisation followed by ring opening to energised CH(2)=NCH(2)O which may fragment to yield CH(2)N and CH(2)O.
- Published
- 2009
337. A novel synthesis of 1,2,3,4-tetrahydrobenz[g]isoquinoline-5,10-diones, 2-aza-anthraquinones and benzo[f]isoindole-4,9-diones
- Author
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Deblander, Jurgen, Abbaspour Tehrani, Kourosch, Department of Bio-engineering Sciences, and Organic Chemistry
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napthoquinone ,2-azaanthraquinones ,napthalene ,ring closure - Abstract
Quinones are an important class of naturally occurring compounds, which demonstrate antimicrobial and anticancer activities. In view of their biological activity, especially the quinones bearing N-heterocyclic rings have elicited considerable interest. Tetrahydroisoquinoline-5,8-diones and isoquinoline-5,8-diones have been used as a structural template for the synthesis of naturally occurring potent antibiotics such as saframycins, lemonomycin and bostrycoidin. Also the isoindole analogues, such as bhimamycin C and bhimamycin D, display a wide range of biological effects. Although the (tetrahydro)benzo[g]isoquinoline-5,10-diones and benzo[f]isoindole-4,9-diones have attracted considerable attention in literature, to date only a limited number of synthetic pathways was developed, and none of these addresses the construction of 2-substituted 1,2,3,4-tetrahydro-benz[g]isoquinoline-5,10-diones. We developed a general synthetic strategy for these classes of compounds, which consists of the synthesis of a 1,4-naphthoquinone (or a 1,4-dimethoxynaphthalene in case of 1,2,3,4-tetrahydrobenz[g]isoquinoline-5,10-diones), containing a N-protected aminoalkyl group at C-3 and a leaving group at the C-2-methylene group. An intramolecular substitution, an optional N-alkylation and a subsequent oxidation afford the desired target compounds.
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- 2008
338. Synthesis of 2,3,6,7-tetrabromoanthracene
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Friederike Herrmann, Jochen Mattay, and Christian Schäfer
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Anthracene ,arenes ,polycycles ,Organic Chemistry ,cyclizations ,Convergent synthesis ,anthracene ,7-tetrabromoanthracene ,Nanotechnology ,ring closure ,2,3,6,7-tetrabromoanthracene ,Full Research Paper ,lcsh:QD241-441 ,Chemistry ,chemistry.chemical_compound ,lcsh:Organic chemistry ,chemistry ,Computational chemistry ,lcsh:Q ,lcsh:Science ,Benzene - Abstract
Summary The first synthesis of 2,3,6,7-tetrabromoanthracene is presented, starting from benzene in a straightforward four step synthesis.
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- 2008
339. Novel synthesis of naphthopyranoisoxazoles and versatile access to naphthopyranoisoxazolines
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Theodoros Liaskopoulos, Stavroula Skoulika, George Varvounis, and Petros G. Tsoungas
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Nitrile ,Iodide ,chemistry.chemical_element ,route ,ring closure ,in-vitro ,Iodine ,Medicinal chemistry ,Catalysis ,cycloadditions ,chemistry.chemical_compound ,halogenation ,Organic chemistry ,antimicrobial activities ,Triethylamine ,chemistry.chemical_classification ,heterocycles ,Chemistry ,Alkene ,Organic Chemistry ,oxidations ,biological evaluation ,Halogenation ,isoxazolines ,natural-products ,Oxime ,Sodium hypochlorite ,nitrile oxides ,derivatives ,potent ,1,3-dipolar cycloaddition reactions - Abstract
2-(Alkenyloxy)naphthalene-l-carbaldehyde oximes are oxidized with potassium iodide, iodine and sodium bicarbonate directly to novel naphthopyranoisoxazoles. Naphthopyranoisoxazoles are also prepared from 2-(3-chloroallyloxy)napbthalene-1-carbaldehyde oxime or 2-(alkynyloxy)naphthalene-1-carbaldehyde oximes by oxidation with sodium hypochlorite and triethylamine. The oxidation of 2-(alkenyloxy)naphthatene-1-carbaldehyde oximes with sodium hypochlorite and triethylamine afforded novel naphthopyranoisoxazolines. The former reaction is tentatively proposed to occur via activation of the alkene side chain by means of an iodonium intermediate and either 1,3-dipolar interaction with a nitrile oxide side-group or cyclization with a hydroximic acid iodide side-group. Synthesis-Stuttgart
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- 2008
340. Synthesis of a conformationally constrained phenylalanine derivative by a strategic combination of ring-closing enyne metathesis and Diels-Alder reaction
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Sambasivarao Kotha and Priti Khedkar
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Peptide Antagonists ,Design ,Stereochemistry ,Constrained Amino Acid ,Phenylalanine ,Metathesis ,Enyne metathesis ,Ring (chemistry) ,Catalysis ,chemistry.chemical_compound ,Diets-Alder ,Diels alder ,Heck Cyclizations ,Diels–Alder reaction ,Acid Tic Derivatives ,Amino-Acids ,Asymmetric-Synthesis ,Napieralski Reaction ,Organic Chemistry ,1,2,3,4-Tetrahydroisoquinoline-3-Carboxylic Acid ,chemistry ,Ring Closure ,Pictet-Spengler Reaction ,Derivative (chemistry) ,Receptor - Abstract
An efficient route towards the synthesis of a conformationally constrained phenylalanine derivative is demonstrated using the strategic combination of ring-closing enyne metathesis and Diels-Alder reaction as key steps.
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- 2008
341. Hydroxylamine Oxygen as Nucleophile in Palladium(0)- and Palladium(II)-Catalyzed Allylic Alkylation: A Novel Access to Isoxazolidines
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Giovanni Poli, Guillaume Prestat, Pedro Merino, Tomás Tejero, Vanni Mannucci, David Madec, Ministerio de Educación y Ciencia (España), and Gobierno de Aragón
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Reaction conditions ,Organic Chemistry ,chemistry.chemical_element ,General Medicine ,Hydroxylamines ,Medicinal chemistry ,Oxygen ,Catalysis ,chemistry.chemical_compound ,Tsuji–Trost reaction ,Hydroxylamine ,chemistry ,Nucleophile ,Intramolecular force ,Allyl complexes ,Organic chemistry ,Isoxazolidines ,Palladium ,Ring closure - Abstract
5 pages.-- et al., In search for novel heterocyclization processes, the intramolecular Pd-mediated allylic alkylation of homoallyl hydroxylamines is described. Depending on both the reaction conditions and the substrates, cis- or trans-3-substituted-5-vinyl isoxazolidines are preferentially obtained. The corresponding starting materials for the cyclization step are readily obtained through cross-metathesis of the easily accessible unsubstituted homoallyl hydroxylamines., This study was supported by the Ministerio de Educacion y Ciencia (MEC) and FEDER Program (Madrid, Spain, project CTQ2004-0421/BQU) and the Gobierno de Aragón (Zaragoza, Spain). V.M. thanks MEC for a FPU predoctoral grant.
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- 2007
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342. Palladium-Catalyzed Construction of Polycyclic Heterocycles by an Alkyne Insertion and Direct Arylation Cascade
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30322192, 60109014, Ohno, Hiroaki, Yamamoto, Mio, Iuchi, Mutsumi, Fujii, Nobutaka, Tanaka, Tetsuaki, 30322192, 60109014, Ohno, Hiroaki, Yamamoto, Mio, Iuchi, Mutsumi, Fujii, Nobutaka, and Tanaka, Tetsuaki
- Abstract
Cascade cyclization of bromoenynes bearing an aryl group with catalytic amounts of palladium(II) acetate and cesium carbonate led to the direct construction of tri- or tetracyclic heterocycles. Direct arylation of a pyrrole, furan or thiophene ring in the cascade reaction affords the corresponding fused heteroarenes in moderate to good yields.
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- 2011
343. Interaction of smectites with organic photochromic compounds
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Adams, J. M. and Gabbutt, A. J.
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- 1990
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344. Hydrosilylation-Metathesis Sequence Leading to 1-Silaindenes
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70512755, 20174279, Matsuda, Takanori, Yamaguchi, Yoshiyuki, Ishida, Naoki, Murakami, Masahiro, 70512755, 20174279, Matsuda, Takanori, Yamaguchi, Yoshiyuki, Ishida, Naoki, and Murakami, Masahiro
- Published
- 2010
345. Synthetic and theoretical studies of novel ring closure and ring opening reactions
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Sepúlveda Argués, José and González Rosende, Mª Eugenia
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Transamidation reaction ,UNESCO::QUÍMICA ,Michael addition ,QUÍMICA::Química orgánica [UNESCO] ,Ring opening ,UNESCO::QUÍMICA::Química orgánica ,Imidazopyrimidines ,Guanidines ,Ring closure ,QUÍMICA [UNESCO] - Abstract
Ring closure and ring opening reactions are in many cases useful synthetic procedures in organic chemistry. They allow the preparation of complex molecules with high stereoselectivity and good yields. Mechanistic and theoretical studies have been carried out on the transformation of 2-aminopyrimidines into imidazo[1,2-c]pyrimidines and guanidines, respectively, through ring closure and ring opening reactions, as well as the transamidation reactions through the ring closure and ring opening of guanidine derivatives, which constitute novel synthetic methods. Sepulveda Arques, Jose, Jose.Sepulveda@uv.es
- Published
- 2006
346. Gold(I)-Catalyzed Formation of 5-Methylene-oxazolidin-2-ones
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Buzas, Andréa, Gagosz, Fabien, Laboratoire de synthèse organique (DCSO), and École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
- Subjects
oxazolidinones ,[CHIM.ORGA]Chemical Sciences/Organic chemistry ,ring closure ,gold catalysis - Abstract
communication; International audience; A study concerning the gold(I) catalyzed rearrangement of propargylic tert-butylcarbamates into 5-methylene-oxazolidin-2-ones is described. The mild reaction conditions employed allow the efficient synthesis of a variety of these structures which would be less conveniently obtained using other reported methods.
- Published
- 2006
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347. alpha-EWG-Substituted Enones: Suitable Substrates for Ring-Closing Metathesis
- Author
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Toueg, Julie, Prunet, Joëlle, Laboratoire de synthèse organique (DCSO), and École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
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natural products ,[CHIM.ORGA]Chemical Sciences/Organic chemistry ,metathesis ,ring closure ,enones - Abstract
The A ring of hexacyclinic acid has been synthesised, using a ring-closing metathesis involving an alpha-EWG-substituted enone as the key step. We have then explored the scope of this reaction, which gives access to various 5- and 6-membered rings.
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- 2006
348. New Route to 3-Alkylthiazolo[3,2-a]benzimidazole Derivatives
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Christian Roussel, Nicolas Vanthuyne, Maria Hristova, Mihaela Roman, Federico Andreoli, and Aix Marseille Université (AMU)
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Benzimidazole ,Pharmaceutical Science ,ring closure ,010402 general chemistry ,Ring (chemistry) ,01 natural sciences ,Models, Biological ,Article ,Analytical Chemistry ,lcsh:QD241-441 ,chemistry.chemical_compound ,lcsh:Organic chemistry ,Heterocyclic Compounds ,Drug Discovery ,[CHIM]Chemical Sciences ,Physical and Theoretical Chemistry ,Thiazole ,ComputingMilieux_MISCELLANEOUS ,010405 organic chemistry ,Chemistry ,Organic Chemistry ,2-Methylthiothiazolium salts ,Combinatorial chemistry ,3. Good health ,0104 chemical sciences ,Chemistry (miscellaneous) ,Electrophile ,Propargyl ,Molecular Medicine ,fused heterocycles ,Benzimidazoles - Abstract
3-Alkyl-thiazolo[3,2-a]benzimidazole derivatives are obtained in high yields via the corresponding 4-alkyl- N -3-(2-aminophenyl)-thiazoline-2-thiones which are easily prepared from 1,2-diaminobenzene, CS 2 and halogenoketones. This new route compares advantageously with the classical mercaptobenzimidazole routes in term of simplicity, isolated yields and availability of the starting materials. Keywords: 2-Methylthiothiazolium salts, fused heterocycles, ring closure. Introduction 3-Methyl-thiazolo[3,2-a]benzimidazole ( 1a ) is available for screening purposes in three libraries according to Chem. Abstracts. So far the reported synthetic routes leading to thiazolo[3,2-a]benzimidazole skeleton begin from the preformed 2-mercaptobenzimidazole which is condensed at the mercapto-group with various electrophiles such as alpha-haloketones [1], propargyl halides [2] or 1,2,3-tribromopropane [3] followed by cyclization to form the thiazole ring in the last step (Scheme 1). Scheme 1 NNSR
- Published
- 2005
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349. Chiral succinate: A precursor for enantiomerically pure beta(2)-amino acids
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Arvydas Stoncius, Norbert Sewald, and Markus Nahrwold
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chemistry.chemical_classification ,Stereochemistry ,organic chemicals ,Organic Chemistry ,Regioselectivity ,ring closure ,Catalysis ,Amino acid ,beta-amino acids ,chemistry ,regioselectivity ,polycyclic compounds ,Organic chemistry ,rearrangements ,heterocyclic compounds ,Beta (finance) ,stereoselective synthesis - Abstract
Five suitably protected enantiomerically pure beta(2)-amino acids, homologues of proteinogenic alpha-amino acids, were synthesized from the common chiral precursor, tert-butyl succinyloxazolidinone.
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- 2005
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350. Síntesis de análogos rígidos de hormonas esteroidales
- Author
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Joselevich, María and Ghini, Alberto A.
- Subjects
RIGIDEZ CONFORMACIONAL ,HOMOLOGACION ,CARBON BRIDGES ,RING CLOSURE ,CICLACION ,STEROIDAL HORMONES ,HOMOLOGATION ,CONFORMATIONAL RIGIDITY ,HORMONAS ESTEROIDALES ,PUENTES CARBONADOS - Abstract
En esta tesis se describe la síntesis de análogos de hormonas esteroidales con estructuras conformacionalmente rígidas, debido a la presencia de un anillo adicional que incluye al carbono neopentílico de la posición 19 (metilo angular). Los esteroides sintetizados fueron 6,19-metanoprogesterona y 19(S)-metil-11,19-óxidoprogesterona. Las etapas clave para ambas síntesis fueron: i) funcionalización remota del metilo-19 realizada por medio de una reacción radicalaria desde un grupo hidroxilo ubicado en la posición 6β; ii) homologación de la posición neopentílica para generar un carbono adicional adecuadamente funcionalizado (C-19a); iii) formación del ciclo propiamente dicho. Para la etapa de homologación (reacción de Wittig) en la síntesis de 6,19-metanoprogesterona se desarrollaron condiciones libres de sales que permitieron la obtención de rendimientos excelentes, notablemente superiores a los descriptos para esa reacción en sustratos similares. Para la formación del puente 6,19-metano se utilizó una reacción de adición del doble enlace 5,6 sobre el carbono carbonílico incorporado en la etapa anterior (C-19a) catalizada por ácido de Lewis (reacción de Prins) la cual permitió realizar una ciclación 5-endo trig, no favorecida de acuerdo con las reglas de Baldwin. Se realizaron dos aproximaciones a la formación de puentes carbonados entre las posiciones 11 y 19. En la primera (vía iónica) se siguió la estrategia anterior utilizando como precursor para la ciclación 3β-acetiloxi-19-metilidén-5-pregnen-11,20-diona. Se obtuvo finalmente 19(S)- metil-11,19-óxidoprogesterona. En la segunda aproximación (vía radicalaria) se sintetizó el precursor 19-metilidén-3β-terbutildimetilsililoxi-11α-metiltiotiocarboniloxi-5- pregnen-20-ona y se intentó la ciclación por ataque del carbono radicálico generado en C- 11 sobre el carbono vinílico (C-19a) en diferentes condiciones experimentales (solvente, temperatura, concentración, transportados de radicales). Finalmente, se describen los ensayos biológicos realizados con 19(S)-metil-11,19-óxidoprogesterona (actividad mineralocorticoidea) y otros esteroides sintetizados durante este trabajo de tesis(actividad antiherpética). This thesis describes the synthesis of two analogues of steroidal hormones with conformationally rigid structures, owing to the presence of an additional ring that includes the neopentylic carbon at C-19 (angular methyl). The steroids synthesized were 6,19-methanoprogesterone and 19(S)-methyl-11,19-oxidoprogesterone. The key synthetic steps in both cases were: i. remote functionalization of the C-19 methyl from the 6β- hydroxyl group by means of a radical reaction; ii. homologation at the neopentylic position to generate an additional carbon adequately functionalized (C-19a); iii. Formation of the additional ring. The salt-free conditions developed for the homologation step (Wittig reaction) in the synthesis of 6,19-methanoprogesterone gave excellent yields, superior to those described in the literature with similar substrates. For the formation of the 6,19-methano bridge, the addition (catalyzed by a Lewis acid) of the 5,6-double bond onto the carbonylic carbon incorporated in the previous step (C-19a) was used. This reaction allowed a 5-endo trig ring closure, that is disfavored according to the Baldwin rules. Two approximations to the synthesis of 11,19-carbon bridged steroids were done. In the first one (ionic pathway) the same strategy described above was followed; 3β- acetyloxy-19-methylidene-5-pregnen-11,20-dione was used as starting material for the ring closure step. In this route, 19(S)-methyl-11,19-oxidoprogesterone was obtained. In the second approximation (radical pathway), 19-methylidene-3β-terbutyldimethylsilyloxy -11α-methyltiocarbonyloxy-5-pregnene-20-one was synthesized and the ring closure was attempted by attack of the radical carbon generated at C-11 onto the C-19a (vinyl) carbon in different conditions (solvent, temperature, concentration, and radical carrier). Finally, the biological test for 19(S)-methyl-11,19-oxidoprogesterone (mineralocorticoid activity) and other steroids synthesized in this thesis (antiherpetic activity) is described. Fil: Joselevich, María. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina.
- Published
- 2005
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