Asymmetric induction on isocyanide-based transformations: development of stereoselective Ugi-type reactions
Autor(a) principal: | |
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Data de Publicação: | 2023 |
Tipo de documento: | Tese |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/18189 |
Resumo: | The design of new synthetic transformations that rapidly allow construction of structurally complex molecules from simple starting materials under both concepts of diversity and function-oriented syntheses is extremely desirable in contemporary organic chemistry. In this regard, multicomponent reactions (MCRs) appear as one of the most useful strategies for quickly generating structural diversity and molecular complexity. Among the vast repertoire of MCRs, isocyanide-based multicomponent reactions (IMCRs) stand out as a powerful approach to achieve highly functionalized molecules with elevated chemical efficiency, convergence and atom economy. As part of our ongoing interest in developing diastereoselective intramolecular I-MCRs based on chiral scaffolds, an efficient strategy has been established, which combines the stereocontrol of organocatalysis with the diversity-generating character of multicomponent reactions, leading to structurally unique cyclopentenyl frameworks containing two stereogenic centers. Based on our recent success into using hemiacetals in substrate-controlled I-MCR reactions, we have envisioned the development of an asymmetric Ugi-type Reaction with achiral hemiacetals using an organocatalytic Brønsted acid as the element of asymmetric induction. After a short screening of conditions, we found out that SPINOL-derived chiral phosphoric acids, especially with phenanthryl as substituent (59% yield, 66% ee), which was chosen as the best catalyst in this initial screening. |
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Silva, Vitor Alcantara Fernandes daPaixão, Márcio Weberhttp://lattes.cnpq.br/3773908504964104http://lattes.cnpq.br/7490678528488396https://orcid.org/0000-0002-1412-9863https://orcid.org/0000-0002-0421-2831887aabb1-281e-442d-9237-4c99054ba09f2023-06-23T14:56:31Z2023-06-23T14:56:31Z2023-05-26SILVA, Vitor Alcantara Fernandes da. Asymmetric induction on isocyanide-based transformations: development of stereoselective Ugi-type reactions. 2023. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2023. Disponível em: https://repositorio.ufscar.br/handle/ufscar/18189.https://repositorio.ufscar.br/handle/ufscar/18189The design of new synthetic transformations that rapidly allow construction of structurally complex molecules from simple starting materials under both concepts of diversity and function-oriented syntheses is extremely desirable in contemporary organic chemistry. In this regard, multicomponent reactions (MCRs) appear as one of the most useful strategies for quickly generating structural diversity and molecular complexity. Among the vast repertoire of MCRs, isocyanide-based multicomponent reactions (IMCRs) stand out as a powerful approach to achieve highly functionalized molecules with elevated chemical efficiency, convergence and atom economy. As part of our ongoing interest in developing diastereoselective intramolecular I-MCRs based on chiral scaffolds, an efficient strategy has been established, which combines the stereocontrol of organocatalysis with the diversity-generating character of multicomponent reactions, leading to structurally unique cyclopentenyl frameworks containing two stereogenic centers. Based on our recent success into using hemiacetals in substrate-controlled I-MCR reactions, we have envisioned the development of an asymmetric Ugi-type Reaction with achiral hemiacetals using an organocatalytic Brønsted acid as the element of asymmetric induction. After a short screening of conditions, we found out that SPINOL-derived chiral phosphoric acids, especially with phenanthryl as substituent (59% yield, 66% ee), which was chosen as the best catalyst in this initial screening.O desenvolvimento de novas transformações sintéticas que permitam a rápida construção de moléculas estruturalmente complexas, a partir de materiais de partida simples sob ambos os conceitos de diversidade e sínteses orientadas a funções, é extremamente desejável na química orgânica contemporânea. Nesse sentido, as reações multicomponentes (MCRs) aparecem como uma das estratégias mais úteis para gerar rapidamente diversidade estrutural e complexidade molecular. Entre o vasto repertório de MCRs, as reações multicomponentes baseadas em isocianeto (IMCRs) se destacam como uma abordagem poderosa para obter moléculas altamente funcionalizadas com elevada eficiência química, convergência e economia atômica. Como parte de nosso interesse contínuo no desenvolvimento de I-MCRs intramoleculares diastereosseletivas por meio de controle de substrato, foi desenvolvida uma estratégia eficiente, que combina o estereocontrole da organocatálise com o caráter gerador de diversidade de reações multicomponentes, levando a formação de ciclopentenos tetrassubstituídos contendo dois centros estereogênicos. Ainda, com base em nosso recente sucesso no uso de hemiacetais em reações I-MCR controladas por substrato, vislumbramos o desenvolvimento de uma reação assimétrica do tipo Ugi com hemiacetais aquirais usando um ácido de Brønsted quiral como elemento de indução assimétrica. Após uma breve triagem das condições, descobrimos que os ácidos fosfóricos quirais derivados de SPINOL, especialmente usando fenantril como substituinte (59% de rendimento, 66% ee), foram escolhidos como o melhor catalisador nesta triagem inicial.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Processo nº 2019/01973-9, Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Processo nº 2021/10246-3, Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Processo nº 141828/2018-8, Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)engUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarAttribution 3.0 Brazilhttp://creativecommons.org/licenses/by/3.0/br/info:eu-repo/semantics/openAccessOrganocatáliseReação MulticomponenteReação de UgiHemiacetalIsocianetoTransformações estereosseletivasIndução de assimetriaÁcido fosfórico quiralOrganocatalysisUgi reactionIsocyanideMulticomponent reactionStereoselective transformationsAsymmetric inductionChiral Phosphoric AcidCIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICAAsymmetric induction on isocyanide-based transformations: development of stereoselective Ugi-type reactionsIndução assimétrica em transformações baseadas em isocianetos: desenvolvimento de reações estereosseletivas tipo Ugiinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesis600600c9d783c2-174c-4a51-9643-0e44f6fc9ac9reponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALTeseDoutorado.pdfTeseDoutorado.pdfTese de doutoradoapplication/pdf15346147https://repositorio.ufscar.br/bitstream/ufscar/18189/1/TeseDoutorado.pdf5d37a71e7b3527916f9c270cec19e5a9MD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8913https://repositorio.ufscar.br/bitstream/ufscar/18189/2/license_rdf3185b4de2190c2d366d1d324db01f8b8MD52TEXTTeseDoutorado.pdf.txtTeseDoutorado.pdf.txtExtracted texttext/plain291286https://repositorio.ufscar.br/bitstream/ufscar/18189/3/TeseDoutorado.pdf.txteca606341cc449e4715a32db383f8a2cMD53ufscar/181892024-05-14 17:45:43.579oai:repositorio.ufscar.br:ufscar/18189Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222024-05-14T17:45:43Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.eng.fl_str_mv |
Asymmetric induction on isocyanide-based transformations: development of stereoselective Ugi-type reactions |
dc.title.alternative.por.fl_str_mv |
Indução assimétrica em transformações baseadas em isocianetos: desenvolvimento de reações estereosseletivas tipo Ugi |
title |
Asymmetric induction on isocyanide-based transformations: development of stereoselective Ugi-type reactions |
spellingShingle |
Asymmetric induction on isocyanide-based transformations: development of stereoselective Ugi-type reactions Silva, Vitor Alcantara Fernandes da Organocatálise Reação Multicomponente Reação de Ugi Hemiacetal Isocianeto Transformações estereosseletivas Indução de assimetria Ácido fosfórico quiral Organocatalysis Ugi reaction Isocyanide Multicomponent reaction Stereoselective transformations Asymmetric induction Chiral Phosphoric Acid CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICA |
title_short |
Asymmetric induction on isocyanide-based transformations: development of stereoselective Ugi-type reactions |
title_full |
Asymmetric induction on isocyanide-based transformations: development of stereoselective Ugi-type reactions |
title_fullStr |
Asymmetric induction on isocyanide-based transformations: development of stereoselective Ugi-type reactions |
title_full_unstemmed |
Asymmetric induction on isocyanide-based transformations: development of stereoselective Ugi-type reactions |
title_sort |
Asymmetric induction on isocyanide-based transformations: development of stereoselective Ugi-type reactions |
author |
Silva, Vitor Alcantara Fernandes da |
author_facet |
Silva, Vitor Alcantara Fernandes da |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/7490678528488396 |
dc.contributor.authororcid.por.fl_str_mv |
https://orcid.org/0000-0002-1412-9863 |
dc.contributor.advisor1orcid.por.fl_str_mv |
https://orcid.org/0000-0002-0421-2831 |
dc.contributor.author.fl_str_mv |
Silva, Vitor Alcantara Fernandes da |
dc.contributor.advisor1.fl_str_mv |
Paixão, Márcio Weber |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/3773908504964104 |
dc.contributor.authorID.fl_str_mv |
887aabb1-281e-442d-9237-4c99054ba09f |
contributor_str_mv |
Paixão, Márcio Weber |
dc.subject.por.fl_str_mv |
Organocatálise Reação Multicomponente Reação de Ugi Hemiacetal Isocianeto Transformações estereosseletivas Indução de assimetria Ácido fosfórico quiral |
topic |
Organocatálise Reação Multicomponente Reação de Ugi Hemiacetal Isocianeto Transformações estereosseletivas Indução de assimetria Ácido fosfórico quiral Organocatalysis Ugi reaction Isocyanide Multicomponent reaction Stereoselective transformations Asymmetric induction Chiral Phosphoric Acid CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICA |
dc.subject.eng.fl_str_mv |
Organocatalysis Ugi reaction Isocyanide Multicomponent reaction Stereoselective transformations Asymmetric induction Chiral Phosphoric Acid |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICA |
description |
The design of new synthetic transformations that rapidly allow construction of structurally complex molecules from simple starting materials under both concepts of diversity and function-oriented syntheses is extremely desirable in contemporary organic chemistry. In this regard, multicomponent reactions (MCRs) appear as one of the most useful strategies for quickly generating structural diversity and molecular complexity. Among the vast repertoire of MCRs, isocyanide-based multicomponent reactions (IMCRs) stand out as a powerful approach to achieve highly functionalized molecules with elevated chemical efficiency, convergence and atom economy. As part of our ongoing interest in developing diastereoselective intramolecular I-MCRs based on chiral scaffolds, an efficient strategy has been established, which combines the stereocontrol of organocatalysis with the diversity-generating character of multicomponent reactions, leading to structurally unique cyclopentenyl frameworks containing two stereogenic centers. Based on our recent success into using hemiacetals in substrate-controlled I-MCR reactions, we have envisioned the development of an asymmetric Ugi-type Reaction with achiral hemiacetals using an organocatalytic Brønsted acid as the element of asymmetric induction. After a short screening of conditions, we found out that SPINOL-derived chiral phosphoric acids, especially with phenanthryl as substituent (59% yield, 66% ee), which was chosen as the best catalyst in this initial screening. |
publishDate |
2023 |
dc.date.accessioned.fl_str_mv |
2023-06-23T14:56:31Z |
dc.date.available.fl_str_mv |
2023-06-23T14:56:31Z |
dc.date.issued.fl_str_mv |
2023-05-26 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
SILVA, Vitor Alcantara Fernandes da. Asymmetric induction on isocyanide-based transformations: development of stereoselective Ugi-type reactions. 2023. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2023. Disponível em: https://repositorio.ufscar.br/handle/ufscar/18189. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/18189 |
identifier_str_mv |
SILVA, Vitor Alcantara Fernandes da. Asymmetric induction on isocyanide-based transformations: development of stereoselective Ugi-type reactions. 2023. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2023. Disponível em: https://repositorio.ufscar.br/handle/ufscar/18189. |
url |
https://repositorio.ufscar.br/handle/ufscar/18189 |
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eng |
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eng |
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600 600 |
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Attribution 3.0 Brazil http://creativecommons.org/licenses/by/3.0/br/ info:eu-repo/semantics/openAccess |
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Attribution 3.0 Brazil http://creativecommons.org/licenses/by/3.0/br/ |
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openAccess |
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Universidade Federal de São Carlos Câmpus São Carlos |
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Programa de Pós-Graduação em Química - PPGQ |
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UFSCar |
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Universidade Federal de São Carlos Câmpus São Carlos |
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