Publicação
Cu(II) complexes derived from N-carboxymethyl and N-carboxyethyl amino acids as catalysts for asymmetric oxidative coupling of 2-naphthol
| Resumo: | The synthesis, characterization and catalytic performance of chiral Cu(II) complexes derived from N-carboxymethylated and N-carboxyethylated amino acids is reported. The ligand precursors are prepared by single step N-alkylation of the sodium salts of the appropriate chiral amino acid with either sodium chloroacetate or sodium 3-chloropropionate in water. The Cu(II) complexes are obtained upon reaction of Cu(CH3COO)2 with the aqueous or alcoholic suspension of the suitable ligand under vigorous stirring or ultrasound irradiation at room temperature. The Cu(II) compounds are characterised by EPR, UV–vis, circular dichroism and ESI-MS. The molecular structures of two of the prepared complexes are also obtained by single-crystal X-ray diffraction analysis. The catalytic activity of the complexes in the asymmetric oxidative coupling of 2-naphthol is described. All compounds exhibit moderate activity, selectivity and enantioselectivity in ethanol/water mixtures, under aerobic conditions and using potassium iodide as additive. The yields of 1,1′-bi-2-naphthol (BINOL) reached 50% under the optimal conditions, while enantiomeric excesses reached ca. 48%. The effect of variables such as ligand substituents, solvent, temperature and additives on the catalytic activity is also described. In the absence of a base, the complexes only show catalytic activity in the presence of alkali metal iodide such as KI. Details of the oxidative coupling mechanism are studied using spectroscopic and electrochemical methodologies. |
|---|---|
| Autores principais: | Adão, Pedro |
| Outros Autores: | Teixeira, Carlos M.; Carvalho, M. Fernanda N.N.; Kuznetsov, Maxim L.; Gomes, Clara S.B.; Pessoa, João Costa |
| Assunto: | Amino acid Copper 2-Naphthol Oxidative coupling Asymmetric catalysis |
| Ano: | 2019 |
| País: | Portugal |
| Tipo de documento: | artigo |
| Tipo de acesso: | acesso restrito |
| Instituição associada: | Universidade de Leiria e Oeste |
| Idioma: | inglês |
| Origem: | IC-online |
| _version_ | 1877756244268154880 |
|---|---|
| author | Adão, Pedro |
| author2 | Teixeira, Carlos M. Carvalho, M. Fernanda N.N. Kuznetsov, Maxim L. Gomes, Clara S.B. Pessoa, João Costa |
| author2_role | author author author author author |
| author_facet | Adão, Pedro Teixeira, Carlos M. Carvalho, M. Fernanda N.N. Kuznetsov, Maxim L. Gomes, Clara S.B. Pessoa, João Costa |
| author_role | author |
| contributor_name_str_mv | Repositório IC-Online |
| country_str | PT |
| creators_json_txt | [{\"Person.name\":\"Adão, Pedro\",\"Person.identifier.cienciaID\":\"EE10-E159-C859\",\"Person.identifier.orcid\":\"0000-0002-7216-0260\",\"Person.identifier.scopusAuthorID\":\"9535765800\"},{\"Person.name\":\"Teixeira, Carlos M.\"},{\"Person.name\":\"Carvalho, M. Fernanda N.N.\"},{\"Person.name\":\"Kuznetsov, Maxim L.\"},{\"Person.name\":\"Gomes, Clara S.B.\"},{\"Person.name\":\"Pessoa, João Costa\"}] |
| datacite.contributors.contributor.contributorName.fl_str_mv | Repositório IC-Online |
| datacite.creators.creator.creatorName.fl_str_mv | Adão, Pedro Teixeira, Carlos M. Carvalho, M. Fernanda N.N. Kuznetsov, Maxim L. Gomes, Clara S.B. Pessoa, João Costa |
| datacite.date.Accepted.fl_str_mv | 2019-01-01T00:00:00Z |
| datacite.date.available.fl_str_mv | 2020-07-16T10:57:47Z |
| datacite.date.embargoed.fl_str_mv | 2020-07-16T10:57:47Z |
| datacite.rights.fl_str_mv | http://purl.org/coar/access_right/c_16ec |
| datacite.subjects.subject.fl_str_mv | Amino acid Copper 2-Naphthol Oxidative coupling Asymmetric catalysis |
| datacite.titles.title.fl_str_mv | Cu(II) complexes derived from N-carboxymethyl and N-carboxyethyl amino acids as catalysts for asymmetric oxidative coupling of 2-naphthol |
| dc.contributor.none.fl_str_mv | Repositório IC-Online |
| dc.creator.none.fl_str_mv | Adão, Pedro Teixeira, Carlos M. Carvalho, M. Fernanda N.N. Kuznetsov, Maxim L. Gomes, Clara S.B. Pessoa, João Costa |
| dc.date.Accepted.fl_str_mv | 2019-01-01T00:00:00Z |
| dc.date.available.fl_str_mv | 2020-07-16T10:57:47Z |
| dc.date.embargoed.fl_str_mv | 2020-07-16T10:57:47Z |
| dc.format.none.fl_str_mv | application/pdf |
| dc.identifier.none.fl_str_mv | http://hdl.handle.net/10400.8/5012 |
| dc.language.none.fl_str_mv | eng |
| dc.publisher.none.fl_str_mv | Elsevier |
| dc.rights.cclincense.fl_str_mv | http://creativecommons.org/licenses/by-nc-nd/4.0/ |
| dc.rights.none.fl_str_mv | http://purl.org/coar/access_right/c_16ec |
| dc.subject.none.fl_str_mv | Amino acid Copper 2-Naphthol Oxidative coupling Asymmetric catalysis |
| dc.title.fl_str_mv | Cu(II) complexes derived from N-carboxymethyl and N-carboxyethyl amino acids as catalysts for asymmetric oxidative coupling of 2-naphthol |
| dc.type.none.fl_str_mv | http://purl.org/coar/resource_type/c_6501 |
| description | The synthesis, characterization and catalytic performance of chiral Cu(II) complexes derived from N-carboxymethylated and N-carboxyethylated amino acids is reported. The ligand precursors are prepared by single step N-alkylation of the sodium salts of the appropriate chiral amino acid with either sodium chloroacetate or sodium 3-chloropropionate in water. The Cu(II) complexes are obtained upon reaction of Cu(CH3COO)2 with the aqueous or alcoholic suspension of the suitable ligand under vigorous stirring or ultrasound irradiation at room temperature. The Cu(II) compounds are characterised by EPR, UV–vis, circular dichroism and ESI-MS. The molecular structures of two of the prepared complexes are also obtained by single-crystal X-ray diffraction analysis. The catalytic activity of the complexes in the asymmetric oxidative coupling of 2-naphthol is described. All compounds exhibit moderate activity, selectivity and enantioselectivity in ethanol/water mixtures, under aerobic conditions and using potassium iodide as additive. The yields of 1,1′-bi-2-naphthol (BINOL) reached 50% under the optimal conditions, while enantiomeric excesses reached ca. 48%. The effect of variables such as ligand substituents, solvent, temperature and additives on the catalytic activity is also described. In the absence of a base, the complexes only show catalytic activity in the presence of alkali metal iodide such as KI. Details of the oxidative coupling mechanism are studied using spectroscopic and electrochemical methodologies. |
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| eu_rights_str_mv | restrictedAccess |
| format | article |
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| institution | Universidade de Leiria e Oeste |
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| language | eng |
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| person_str_mv | Adão, Pedro Adão, Pedro https://www.ciencia-id.pt/EE10-E159-C859 EE10-E159-C859 http://orcid.org/0000-0002-7216-0260 0000-0002-7216-0260 Teixeira, Carlos M. Carvalho, M. Fernanda N.N. Kuznetsov, Maxim L. Gomes, Clara S.B. Pessoa, João Costa |
| publishDate | 2019 |
| publisher.none.fl_str_mv | Elsevier |
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| spelling | engElsevierpt_PTThe synthesis, characterization and catalytic performance of chiral Cu(II) complexes derived from N-carboxymethylated and N-carboxyethylated amino acids is reported. The ligand precursors are prepared by single step N-alkylation of the sodium salts of the appropriate chiral amino acid with either sodium chloroacetate or sodium 3-chloropropionate in water. The Cu(II) complexes are obtained upon reaction of Cu(CH3COO)2 with the aqueous or alcoholic suspension of the suitable ligand under vigorous stirring or ultrasound irradiation at room temperature. The Cu(II) compounds are characterised by EPR, UV–vis, circular dichroism and ESI-MS. The molecular structures of two of the prepared complexes are also obtained by single-crystal X-ray diffraction analysis. The catalytic activity of the complexes in the asymmetric oxidative coupling of 2-naphthol is described. All compounds exhibit moderate activity, selectivity and enantioselectivity in ethanol/water mixtures, under aerobic conditions and using potassium iodide as additive. The yields of 1,1′-bi-2-naphthol (BINOL) reached 50% under the optimal conditions, while enantiomeric excesses reached ca. 48%. The effect of variables such as ligand substituents, solvent, temperature and additives on the catalytic activity is also described. In the absence of a base, the complexes only show catalytic activity in the presence of alkali metal iodide such as KI. Details of the oxidative coupling mechanism are studied using spectroscopic and electrochemical methodologies.application/pdfpt_PTCu(II) complexes derived from N-carboxymethyl and N-carboxyethyl amino acids as catalysts for asymmetric oxidative coupling of 2-naphtholPersonalAdão, PedroDSpacehttp://dspace.org/items/229a385b-0a6c-4817-9518-f2f58fabdb54DSpacehttp://dspace.org/items/229a385b-0a6c-4817-9518-f2f58fabdb54AdãoPedroCiência IDhttps://www.ciencia-id.ptEE10-E159-C859ORCIDhttp://orcid.org0000-0002-7216-0260Scopus Author IDhttps://www.scopus.com9535765800Teixeira, Carlos M.Carvalho, M. Fernanda N.N.Kuznetsov, Maxim L.Gomes, Clara S.B.Pessoa, João CostaHostingInstitutionOrganizationalRepositório IC-Onlinee-mailmailto:repositorio@ulo.ptrepositorio@ulo.ptISSNIsPartOf2468-8231DOIIsPartOfoi.org/10.1016/j.mcat.2019.1104802020-07-16T10:57:47Z20192019-01-01T00:00:00ZHandlehttp://hdl.handle.net/10400.8/5012http://purl.org/coar/access_right/c_16ecrestricted accessAmino acidCopper2-NaphtholOxidative couplingAsymmetric catalysis945557 bytesFundação para a Ciência e a TecnologiaNovos Materiais Organometálicos Luminescentes: Preparação, Propriedades Fotofísicas e Aplicações em Díodos Emissores de Luz de Elevada Eficiênciainfo:eu-repo/grantAgreement/FCT//SFRH%2FBPD%2F107834%2F2015/PTSFRH/BPD/107834/2015Crossref Funder IDhttp://doi.org/10.13039/501100001871Fundação para a Ciência e a TecnologiaDEVELOPMENT OF NEW RECYCLABLE AND WIDELY APPLICABLE HETEROGENEOUS CATALYSTS FOR CATALYTIC OXIDATIONS AND REDUCTIONSinfo:eu-repo/grantAgreement/FCT//SFRH%2FBPD%2F79778%2F2011/PTSFRH/BPD/79778/2011Crossref Funder IDhttp://doi.org/10.13039/501100001871Fundação para a Ciência e a TecnologiaAminoacid-derived transition metal complexes as C-C bond forming and C-H activation catalystsinfo:eu-repo/grantAgreement/FCT//PD%2FBD%2F106078%2F2015/PTPD/BD/106078/2015Crossref Funder IDhttp://doi.org/10.13039/501100001871Fundação para a Ciência e a TecnologiaMARE - Marine and Environmental Sciences Centreinfo:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UID%2FMAR%2F04292%2F2019/PTUID/MAR/04292/20196817 - DCRRNI IDCrossref Funder IDhttp://doi.org/10.13039/501100001871Fundação para a Ciência e a TecnologiaAssociated Laboratory for Green Chemistry - Clean Technologies and Processesinfo:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UID%2FQUI%2F50006%2F2019/PTUID/QUI/50006/20196817 - DCRRNI IDCrossref Funder IDhttp://doi.org/10.13039/501100001871literaturehttp://purl.org/coar/resource_type/c_6501journal article2019http://creativecommons.org/licenses/by-nc-nd/4.0/http://purl.org/coar/access_right/c_16ecapplication/pdffulltexthttps://iconline.ulo.pt/bitstreams/e130b31b-c8b9-429b-b424-1af22daea0cf/downloadMolecular Catalysis475 |
| spellingShingle | Cu(II) complexes derived from N-carboxymethyl and N-carboxyethyl amino acids as catalysts for asymmetric oxidative coupling of 2-naphthol Adão, Pedro Amino acid Copper 2-Naphthol Oxidative coupling Asymmetric catalysis |
| status | SINGLETON |
| subject.fl_str_mv | Amino acid Copper 2-Naphthol Oxidative coupling Asymmetric catalysis |
| title | Cu(II) complexes derived from N-carboxymethyl and N-carboxyethyl amino acids as catalysts for asymmetric oxidative coupling of 2-naphthol |
| title_full | Cu(II) complexes derived from N-carboxymethyl and N-carboxyethyl amino acids as catalysts for asymmetric oxidative coupling of 2-naphthol |
| title_fullStr | Cu(II) complexes derived from N-carboxymethyl and N-carboxyethyl amino acids as catalysts for asymmetric oxidative coupling of 2-naphthol |
| title_full_unstemmed | Cu(II) complexes derived from N-carboxymethyl and N-carboxyethyl amino acids as catalysts for asymmetric oxidative coupling of 2-naphthol |
| title_short | Cu(II) complexes derived from N-carboxymethyl and N-carboxyethyl amino acids as catalysts for asymmetric oxidative coupling of 2-naphthol |
| title_sort | Cu(II) complexes derived from N-carboxymethyl and N-carboxyethyl amino acids as catalysts for asymmetric oxidative coupling of 2-naphthol |
| topic | Amino acid Copper 2-Naphthol Oxidative coupling Asymmetric catalysis |
| topic_facet | Amino acid Copper 2-Naphthol Oxidative coupling Asymmetric catalysis |
| url | http://hdl.handle.net/10400.8/5012 |
| visible | 1 |