Contribuição ao estudo de reações mediadas por calcogenetos Zn e Cu: hidrocalcogenação de ácidos e ésteres e síntese de sulfetos arílicos

Página do item simplificado
dc.contributor.advisor1Barros, Olga Soares do Rêgo
dc.contributor.advisor1Latteshttp://lattes.cnpq.br/8311808341863723por
dc.contributor.referee1Barros, Olga Soares do Rêgo
dc.contributor.referee2Souza, Aparecido Ribeiro de
dc.contributor.referee3Vasconcellos, Mário Luiz Araújo de Almeida
dc.creatorNunes, Vanessa Loren
dc.creator.Latteshttp://lattes.cnpq.br/3611308478246793por
dc.date.accessioned2014-09-19T11:28:41Z
dc.date.issued2012-05-04
dc.description.abstractThis work describes some studies on the preparation of unsymmetrical diaryl thioethers catalyzed by Copper(I)-Senelenophene-2-carboxylate. The results concern to the catalyzed cross-coupling reaction between aryl halides and aryl or alkylthiols using Copper(I)-Senelenophene-2-carboxylate (CuSC) a new Cu-catalyzed one-pot protocol. The products were obtained in good to excellent yields under relatively mild reaction conditions presenting chemoselectivity and functional group tolerance. Additionally, we have developed a chemio-, regio and stereoselective synthesis of vinyl chalcogenides compounds promoted by zinc chalcogenolates. In this protocol the reductive cleavage of chalcogen bond by the Zn/NH4OH system led to zinc chalcogenolates. The reaction was carried out with acids and esters propiolics afford β-chalcogenacrillic acids and esters under mild and basic conditions. The stereochemistry corresponding to anti-Markovnikov addition of the chalcogenolate constituents across the triple bond were obtained in good yields.eng
dc.description.provenanceSubmitted by Erika Demachki (erikademachki@gmail.com) on 2014-09-18T18:51:43Z No. of bitstreams: 2 Dissertação Vanessa Loren Nunes.pdf: 10979785 bytes, checksum: 8efff856842f8d2962b9f8221ec1fcb5 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5)eng
dc.description.provenanceApproved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2014-09-19T11:28:41Z (GMT) No. of bitstreams: 2 Dissertação Vanessa Loren Nunes.pdf: 10979785 bytes, checksum: 8efff856842f8d2962b9f8221ec1fcb5 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5)eng
dc.description.provenanceMade available in DSpace on 2014-09-19T11:28:41Z (GMT). No. of bitstreams: 2 Dissertação Vanessa Loren Nunes.pdf: 10979785 bytes, checksum: 8efff856842f8d2962b9f8221ec1fcb5 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2012-05-04eng
dc.description.resumoEste trabalho descreve o estudo das reações de acoplamento cruzado entre iodetos arílicos e tióis arílicos ou alquílicos catalisada por 2-carboxilato selenofeno de cobre (I) (CuSC). Apresentamos uma nova metodologia “ one pote” para a síntese de tioésteres arílicos obtidos em condições reacionais relativamente brandas, apresentando quimiosseletividade, tolerância a diversos grupos funcionais e rendimentos que variam entre bons a ótimos (70-100%). R1I + R2SH K3PO4, DMSO S R1 R2 Adicionalmente, desenvolvemos uma síntese quimio, régio, e estereosseletiva de compostos vinil calcogenetos promovida por calcogenolato de zinco. Neste protocolo a clivagem redutiva da ligação calcogênio feita pelo sistema Zn/NH4OH obteve os calcogenolatos de zinco. A reação foi realizada com ácidos e ésteres propiólicos formando ácidos acrílicos β-calcogênio e ésteres sob condições básicas e brandas. A estereoquímica corresponde a adição anti-Markovnikov dos constituintes calcogenolatos através da ligação tripla. Os calcogenetos vinílicos foram obtidos em bons rendimentos (40-96).por
dc.description.sponsorshipConselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqpor
dc.formatapplication/pdf*
dc.identifier.citationNunes, Vanessa Loren. Contribuição ao estudo de reações mediadas por calcogenetos Zn e Cu: hidrocalcogenação de ácidos e ésteres e síntese de sulfetos arílicos. 2012. 117 f. Dissertação (Mestrado em Química) - Universidade Federal de Goiás, Goiânia, 2012.por
dc.identifier.urihttp://repositorio.bc.ufg.br/tede/handle/tede/3097
dc.languageporpor
dc.publisherUniversidade Federal de Goiáspor
dc.publisher.countryBrasilpor
dc.publisher.departmentInstituto de Química - IQ (RG)por
dc.publisher.initialsUFGpor
dc.publisher.programPrograma de Pós-graduação em Química (IQ)por
dc.relation.referencesALEXAKIS, A.; POLET, D.; TISSOT-CROSSET, K. Angew. Chem. Int. Ed. v. 43, p. 2426, 2004. ALEXAKIS, A.; POLET, D. Cu-catalysed asymmetric 1,4-addition of Me3Al to nitroalkenes. Synthesis of (+)-ibuprofen, Tetrahedron Lett. v. 46, p. 1529-1532, 2005. ALEXAKIS, A.; D’ AUGUSTIN, M.; PALAIS, L. Angew. Chem. Int. Ed. v. 44, p. 1376, 2005. BETAGEL, O.; SEIBERT, H. Chem. Ber. v. 65, p. 815, 1932. BRANDSMA, L. Preparative Acetylenic Chemistry. 2ª Edition. Amsterdam, Oxford, New York, Tokyo: Elsevier, 1988. p. 100-101. BIEBER, L. W.; SÁ, A. C. P. F.; MENEZES, P. H.; GONÇALVES, S. M. C. General synthesis of alkyl phenyl selenides from organic halides mediated by zinc in aqueous medium, Tetrahedron Letters, v. 42, p. 4597-4599, 2001. BARROS, O. S. R.; LANG, E. S.; PEPPE, C.; ZENI, G. Indium(I) Iodide-Mediated Chemo-, Regio-, and Stereoselective Hydrotelluration of 2-Alkyn-1-ol Derivatives, Synlett, v. 11, p. 1725-1727, 2003. BACK, T.G. Organoselenium chemistry: a practical approach, University Press: Oxford, 1999. BUCKWALD, S. L.; BLACMOND, D. G.; STRIETER, E. R. The Role of Chelating Diamine Ligands in the Goldberg Reaction: A Kinetic Study on the Copper-Catalyzed Amidation of Aryl Iodides, J. Am. Chem. Soc. v. 127, p. 4120-4121, 2005. BUCKWALD, L. S.; KLAPARS, A.; HUANG, X. A General and Efficient Copper Catalyst for the Amidation of Aryl Halides, J. Am. Chem. Soc. v. 124, p. 7421-7428, 2002. BUCHWALD, S. L; KWONG, F. Y. A General, Efficient, and Inexpensive Catalyst System for the Coupling of Aryl Iodides and Thiols, Org. Lett. v. 4, p. 3517-3520, 2002. COMASSETO, J. V.; PILLI, R. A.; SIMONELLI, F. -“THE BRAZILIAN MEETINGS ON ORGANIC SYNTHESIS (BMOS)” UMA RETROSPECTIVA, J. Braz. Chem. Soc. v. 12, p. 5, 2001. COMASSETO, J. V.; FERREIRA, J. T. B. STEREOSELECTIVE SYNTHESIS OF VINYLIC SELENIDES, J. Org. Chem. v. 216, p. 287-294, 1981. DIECK, H. A.; HECK, F. R. Palladium catalyzed synthesis of aryl, heterocyclic and vinylic acetylene derivatives, J. Organomet. Chem. v. 93, p. 259-263, 1975. DABDOUB, M. J.; DABDOUB, V. B.; PEREIRA, M. A. Hydrochalcogenation of phenylthioacetylenes. Synthesis of mixed (Z)-trisubstituted 1,2-bis(organylchalcogeno)-1-alkenes, Tetrahedron Letters, v. 42, p. 1595-1597, 2001. DABDOUB, M. J.; BARONI, A. C. M.; LENARDÃO, E. J.; GIANETI, T. R.; HURTADO, G. R. Synthesis of (Z)-1-phenylseleno-1,4-diorganyl-1-buten-3-ynes: hydroselenation of symmetrical and unsymmetrical 1,4-diorganyl-1,3-butadiynes, Tetrahedron, v. 57, p. 4271-4276, 2001. DABDOUB, M. J.; CASSOL, T. M.; BATISTA, A. C. F. Regiospecific hydroselenation of terminal acetylenes using aluminum phenylselenolate anion, Tetrahedron Letters, v. 37, p. 9005-9008, 1996. DOWSLAND, J.; MCKERLIE, F.; PROCTER, D. J. Convenient preparation of ytterbium(III) chalcogenolate complexes by insertion of ytterbium into chalcogen-chalcogen bonds. Application in the ring-opening of epoxides, Tetrahedron Lett. v. 41, p. 4923, 2000. FARIAS, R. F. Química de coordenação. 2ª Edição. Campinas, SP: Editora Átomo, 2009. p. 354-355. FALCK, J. R.; PATEL, P. K.; BANDYOPADHYAY, A. Stereospecific Cross-Coupling of α-(Thiocarbamoyl)organostannanes with Alkenyl, Aryl, and Heteroaryl Iodides, J. Am. Chem. Soc. v. 129, p. 790-793, 2007. FKUZAWA, S. I.; NIIMOTO, Y.; FUJINAMI, T.; SAKAI, S. Heteratom Chem. Samarium (II) diiodide-induced reductive cleavage of Se-Se and Te-Te bond in diphenyl diselenide and ditelluride leading to a samarium phenylselenolate and tellurolate: Preparation of unsymmetrical alkylphenyl selenides and tellurides, v. 6, p. 491-495, 1990. GAUTHERON, B.; TAINTURIER, G.; POULY, S.; THEOBALD, F.; VIVIER, H.; LAARIF, A. Trapping of (aryne)metallocene complexes by elemental selenium. Crystal structure of (.eta.5-t-BuC5H4)2ZrSe2C6H4-o, Organometallics, v. 3, p. 1495-1499, 1984. HUANG, Y. Z.; MO, X. S. The Generation of Highly Functionalized Organometallics via Organotellurides and The Stereospecific Preparation of N-Isobutyl 6-Hydroxyl-(2E,4Z)-hexadienamide Derivatives, Synlett , Nº 93, 1998. HUGUET, J. L. Oxidation of Olefins Catalyzed by Selenium, Adv. Chem. v. 76, p. 345-351, 1967. INNITZER, A. Copper(I) Thiophene-2-carboxylate (CuTC), Synlett, Nº 15, p. 2405-2406, 2005. LI, J.J.; GRIBBLE, G.W. in Tetrahedron Organic Chemistry Series, 20 “Palladium in heterocycle chemistry” 2002, U.S.A. LIEBESKIND, L. S; ALLRED, G. D. Copper-Mediated Cross-Coupling of Organostannanes with Organic Iodides at or below Room Temperature, J. Am. Chem. Soc. v. 118, p. 2748-2749, 1996. LIEBESKIND, L.; ZHANG, S.; ZHANG, D.; Ambient Temperature, Ullmann-like Reductive Coupling of Aryl, Heteroaryl, and Alkenyl Halides, J. Org. Chem. v. 62, p. 2312-2313, 1997. LOUIE, J.; HARTWIG, J. F. The Vapor Phase Rearrangement of Thioncarbonates and Thioncarbamates, J. Am. Chem. Soc. v. 117, p. 11598-11599, 1995. KALOGIROS, C.; HADJIARAPOGLOU, L. P. Facile preparation of bicyclo[2.2.2]octenone derivatives via Diels–Alder cycloadditions of in situ-generated masked o-benzoquinones, Tetrahedron, v. 67, p. 3216-3255, 2011. KWART, H.; EVANS, E. R. The Vapor Phase Rearrangement of Thioncarbonates and Thioncarbamates, J. Org. Chem. v. 31, p. 410-413, 1966. KONDO, T.; SHIMIZU, T. Metal-Catalyzed Carbon−Sulfur Bond Formation, Chem. Rev. v. 100, p. 3205-3220, 2000. KOTHA, S.; LAHIRI, K.; KASHINATH, D. Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis, Tetrahedron, v. 58, p. 9633, 2002. MANARIN, F.; ROEHRS, J. A.; GAY, R. M.; BRANDAO, R.; MENEZES, P. H.; NOGUEIRA, C. W.; ZENI, G. Electrophilic Cyclization of 2-Chalcogenealkynylanisoles: Versatile Access to 2-Chalcogen-benzo[b]furans, J. Org. Chem. v. 74, p. 2153-2162, 2009. MIGITA, T.; SHIMIZU, T.; ASAMI, Y.; SHIOBARA, J.; KATO, Y.; KOSUGI, M. The Palladium Catalyzed Nucleophilic Substitution of Aryl Halides by Thiolate Anions, Bull. Chem. Soc. Jpn. v. 53, p. 1385-1389, 1980. MENUIER, P.; GAUTHERON, B.; MAZOUZ, A. Convenient synthesis of new Se,Se′-disubstituted derivatives of benzene-1,2-diselenol, J. Chem. Soc. Chem. Commun, v. 5, p. 424-425, 1986. MIYAURA, N.; YANAGI, T.; SUZUKI, A. Synth. Commun. v. 11, p. 513, 1981. MOVASSAGH, B.; SHAMSIPOOR, M. Stereo- and Regioselective Zinc Mediated Ring-Opening of Epoxides with Diselenides, Synlett, Nº 8, p.1316-1318, 2005. NEGISHI, E.; BABA, S. A Novel Stereospecific Alkenyl-Alkenyl Cross-Coupling by a Palladium- or Nickel-Catalyzed Reaction of Alkenylalanes with Alkenyl Halides, J. Am. Chem. Soc. v. 98, p. 6729-6731, 1976. NEGISHI, E. A genealogy of Pd-catalyzed cross-coupling, J. Organomet. Chem. v. 653, p. 34, 2002. NOGUEIRA, C. W.; ZENI, G.; ROCHA, J. B. T. Organoselenium and Organotellurium Compounds: Toxicology and Pharmacology, Chem. Rev. v. 104, p. 6255-6286, 2004. PALOMO, C.; OIARBIDE, M.; LÓPEZ, R.; GÓMEZ-BENZOA, E. Phosphazene bases for the preparation of biaryl thioethers from aryl iodides and arenethiols, Tetrahedron Lett. v. 41, p. 1283-1286, 2000. PAULMIER, C. Selenium Reagents and Intermediates in Organic Synthesis, Pergamon Press: Oxford, 1986. PETRAGNANI, N. Tellurium in Organic Synthesis. 1ª Edition. London: Elsevier, 1994. REICH, H. J. Organoselenium chemistry. Synthetic transformations based on allyl selenide anions, J. Org. Chem. v. 40, p. 2570-2572, 1975. SLAUGH, L. H. Lithium aluminum hydride, a homogeneous hydrogenation catalyst Tetrahedron, v. 22, p. 1741, 1966. SHARPLESS, K. B.; YOUNG, M. W.; LAUER, R. F. Reactions of selenoxides: Thermal -elimination and H218O exchange, Tetrahedron Lett. v. 14, p. 1979-1982, 1973. SHARPLESS, K. B.; LAUER, R. F. Selenium dioxide oxidation of olefins. Evidence for the intermediacy of allylseleninic acids, J. Am. Chem. Soc. v. 94, p. 7154-7155, 1972. SEVRIN, M.; VAN ENDE, D.; KRIEF, A. Reduction or alkylative reduction of the carbonyl group, Tetrahedron Lett. v. 17, p. 2643-2646, 1976. SEVRIN, M.; DUMONT, W.; HEVESI, L.; KRIEF, A. Transformation of selenides to alkylhalides new routes for homologization of primary alkylhalides, Tetrahedron Lett. v. 17, p. 2647-2650, 1976. SONOGASHIRA, K.; TOHDA, Y.; HAGIRARA, N. A convenient synthesis of acetylenes: catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes and bromopyridines, Tetrahedron Lett. p. 4467-4470, 1975. SCHNEIDER, C. C.; CALDEIRA, H.; GAY, B. M.; BACK, D. F.; ZENI, G. Transmetalation of Z-Telluroenynes: Stereoselective Synthesis of Z-Enynols and Their Application in Palladium-Catalyzed Cyclization, Org. Lett. v. 12, p. 936-939, 2010. SILVEIRA, C. C.; BRAGA, A. L.; VIEIRA, A. S.; ZENI, G. Stereoselective Synthesis of Enynes by Nickel-Catalyzed Cross-Coupling of Divinylic Chalcogenides with Alkynes, J. Org. Chem. v. 68, p. 662-665, 2003. SILVEIRA, C.C.; MENDES, S.R.; ROSA, D.D.; ZENI, G. Cerium(III)-Mediated Efficient and Stereoselective Hydrochalcogenation of Terminal Alkynes, Synthesis, v. 23, p. 4015-4021, 2009. SILVEIRA, C.C.; LARGHI, E.L. Selenium Stabilized Carbenium Ions on Organic Synthesis, J. Braz. Chem. Soc. v. 9, p. 327-340, 1998. STILLE, J. K.; MILSTEIN, D. Palladium-catalyzed coupling of tetraorganotin compounds with aryl and benzyl halides. Synthetic utility and mechanism, J. AM. CHEM. SOC. v. 101, p. 4992-4998, 1979. SCOTT, W. J.; CRISP, G. T.; STILLE, J. K. Palladium-catalyzed coupling of vinyl triflates with organostannanes. A short synthesis of pleraplysillin-1, J. Am. Chem. Soc. v. 106, p. 4630-4632, 1984. SCHOPFER, U.; SCHLAPBACH, A. A general palladium-catalysed synthesis of aromatic and heteroaromatic thioethers, Tetrahedron, v. 57, p. 3069-3073, 2001. TAMAO, K. Discovery of the cross-coupling reaction between Grignard reagents and C(sp2) halides catalyzed by nickel–phosphine complexes, J. Organomet. Chem. v. 653, p. 23, 2002. TAMAO, K.; SUMITANI, K.; KUMADA, M. J. Am. Chem. Soc. v. 94, p. 4374, 1972. TERAO, J.; KAMBE, N.; SONODA, N. Tellurium-zinc exchange reaction. A new preparative method of alkenylzinc reagents, Tetrahedron Lett. v. 37, p. 4741, 1996. VENKATARAMAN, D; BATES, C. G.; GUJADHUR, R. K. A General Method for the Formation of Aryl-Sulfur Bonds Using Copper(I) Catalysts, Org. Lett. v. 4, p. 2803-2806, 2002. WADSWORTH, D. H.; DETTY, M. R. J. Org. Chem, v. 45, p. 4611-4615, 1980. XU, H.; ZHAO, X.; DENG, J.; FU, Y.; FENG, Y. Efficient C–S cross coupling catalyzed by Cu2O, Tetrahedron Letters v. 50, p. 434-437, 2009. XU, X. H.; HUANG, Y. Z. Chin. Chem. Lett., v. 11, p. 473, 2000. XU, X. H.; LIU, W. Q. Chinese Chemical Letters, v. 13, p. 283-284, 2002. XIAO, H.; CHEN, J.; LIU, M.; WU, H.; DING J. An Approach to Disulfide Synthesis Promoted by Sulfonyl Chloride in Sodium Bicarbonate Aqueous Media, Phosphorus, Sulfur, and Silicon, v. 184, p. 2553-2559, 2009. ZHENG, N.; MCWILLIAMS, J. C.; FLEITZ, F. J.; ARMSTRONG III, J. D.; VOLANTE, R. P. Palladium-Catalyzed Synthesis of Aryl Sulfides from Aryl Triflates, J. Org. Chem. v. 63, p. 9606-9607, 1998. ZENI, G.; LÜDTKE, D. S.; PANATIERI, R. B.; BRAGA, A. L. Vinylic Tellurides: From Preparation to Their Applicability in Organic Synthesis, Chem. Rev. v. 106, p. 1032-1076, 2006. ZENI, G.; STRACKE, M. P.; NOGUEIRA, C. W.; BRAGA, A. L.; MENEZES, P. H.; STEFANI, H. A. Hydroselenation of Alkynes by Lithium Butylselenolate: An Approach in the Synthesis of Vinylic Selenides, Organic Letters, v. 6, p. 1135-1138, 2004. ZHU, Y.; XIE, M.; DONG, S.; ZHAO, X.; LIN, L.; LIU, X.; FENG, X. ,Chem. A. European Journal, v.17, p. 8202-8208, 2011.por
dc.rightsAcesso Abertopor
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subjectCompostos organometálicospor
dc.subjectAcoplamento cruzadopor
dc.subjectOrganometalic compoundseng
dc.subjectCross couplingeng
dc.subject.cnpqQUIMICA::QUIMICA ANALITICApor
dc.thumbnail.urlhttp://repositorio.bc.ufg.br/tede/retrieve/8055/Disserta%c3%a7%c3%a3o%20Vanessa%20Loren%20Nunes.pdf.jpg*
dc.titleContribuição ao estudo de reações mediadas por calcogenetos Zn e Cu: hidrocalcogenação de ácidos e ésteres e síntese de sulfetos arílicospor
dc.title.alternativeNew contributions for the synthesis of unsymmetrical diaryl thioethers and vinyl chalcogenides compunds promoted by copper Senelenophene-2-carboxylate and zinc chalcogenolateseng
dc.typeDissertaçãopor

Arquivos

Pacote Original
Agora exibindo 1 - 1 de 1
Imagem de Miniatura
Nome:
Dissertação Vanessa Loren Nunes.pdf
Tamanho:
10.47 MB
Formato:
Adobe Portable Document Format
Descrição:
dissertação
Baixar
Licença do Pacote
Agora exibindo 1 - 1 de 1
Nenhuma Miniatura disponível
Nome:
license.txt
Tamanho:
2.11 KB
Formato:
Item-specific license agreed upon to submission
Descrição:
Baixar

Coleções

Mestrado em Química (IQ)