DYKAT and desymmetrization strategies for the synthesis of axially chiral heterobiaryls
The main objective of this PhD thesis is the development of new methodologies for the synthesis of axially chiral heterobiaryls through asymmetric functionalization of this type of systems. In this regard, the approaches to achieve this goal will be based on a DYKAT (Dynamic Kinetic Asymmetric Trans...
| Autor: | |
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| Tipo de documento: | Tese de doutorado |
| Estado: | Published version |
| Data de publicação: | 2020 |
| País: | España |
| Recursos: | Universidad de Sevilla (US) |
| Repositório: | idUS. Depósito de Investigación de la Universidad de Sevilla |
| OAI Identifier: | oai:idus.us.es:11441/93380 |
| Acesso em linha: | https://hdl.handle.net/11441/93380 |
| Nível de acesso: | Acesso aberto |
| _version_ | 1878733447203127296 |
|---|---|
| author | Romero Arenas, Antonio |
| author_browse | Romero Arenas, Antonio |
| author_facet | Romero Arenas, Antonio |
| author_role | author |
| collection | idUS. Depósito de Investigación de la Universidad de Sevilla |
| description | The main objective of this PhD thesis is the development of new methodologies for the synthesis of axially chiral heterobiaryls through asymmetric functionalization of this type of systems. In this regard, the approaches to achieve this goal will be based on a DYKAT (Dynamic Kinetic Asymmetric Transformation) and a desymmetrization process. Additionally, the synthesised products present a great potential in catalytic applications. In Chapter 1, which severs as an introduction, different strategies for the synthesis of axially chiral heterobiaryls are depicted, focusing on the strategies based on the catalytic asymmetric functionalization of heterobiaryls. On the other hand, in chapter 2, the first of the two developed methodologies during this PhD thesis is described. Thus, this methodology relies on a DYKAT process combined with a Buchwald-Hartwig reaction using racemic and configurationally stable heterobiaryl electrophiles. Then, this protocol has been successfully applied to the synthesis of IAN-type amines in high yields and good to excellent enantioselectivities. In chapter 3, another approach is employed for the synthesis of chiral heterobiaryls. In this case, configurationally labile substrates were desymetrized through an Ir(I)-catalyzed C-H hydroarylation. Thus, this strategy enables the synthesis of heterobiaryls with both axial and central chirality with highly regio-, diastereo- and enantioselectivities. |
| eu_rights_str_mv | openAccess |
| format | doctoralThesis |
| id | ES_5656d34a0103b5afc60145b80c1d0653 |
| institution | Universidad de Sevilla (US) |
| instname_str | Universidad de Sevilla (US) |
| network_acronym_str | ES |
| network_name_str | España |
| oai_identifier_str | oai:idus.us.es:11441/93380 |
| publishDate | 2020 |
| publishDateSort | 2020 |
| reponame_str | idUS. Depósito de Investigación de la Universidad de Sevilla |
| spelling | DYKAT and desymmetrization strategies for the synthesis of axially chiral heterobiaryls Romero Arenas, Antonio The main objective of this PhD thesis is the development of new methodologies for the synthesis of axially chiral heterobiaryls through asymmetric functionalization of this type of systems. In this regard, the approaches to achieve this goal will be based on a DYKAT (Dynamic Kinetic Asymmetric Transformation) and a desymmetrization process. Additionally, the synthesised products present a great potential in catalytic applications. In Chapter 1, which severs as an introduction, different strategies for the synthesis of axially chiral heterobiaryls are depicted, focusing on the strategies based on the catalytic asymmetric functionalization of heterobiaryls. On the other hand, in chapter 2, the first of the two developed methodologies during this PhD thesis is described. Thus, this methodology relies on a DYKAT process combined with a Buchwald-Hartwig reaction using racemic and configurationally stable heterobiaryl electrophiles. Then, this protocol has been successfully applied to the synthesis of IAN-type amines in high yields and good to excellent enantioselectivities. In chapter 3, another approach is employed for the synthesis of chiral heterobiaryls. In this case, configurationally labile substrates were desymetrized through an Ir(I)-catalyzed C-H hydroarylation. Thus, this strategy enables the synthesis of heterobiaryls with both axial and central chirality with highly regio-, diastereo- and enantioselectivities. El objetivo principal de esta tesis doctoral es el desarrollo de nuevas metodologías para la síntesis de heterobiarilos con quiralidad axial a través de la funcionalización asimétrica de este tipo de sistemas. En este sentido, las aproximaciones para cumplir este objetivo se basarán en procesos tipo DYKAT (por sus siglas en inglés: Dynamic Kinetic Asymmetric Transformation) y de desimetrización. Adicionalmente, los productos sintetizados presentan un gran potencial en aplicaciones catalíticas. En el capítulo 1, que sirve de introducción, se presentan diferentes estrategias para la síntesis de heterobiarilos con quiralidad axial, mostrando mayor atención en aquellas basadas en la funcionalización catalítica asimétrica de heterobiarilos. Por otra parte, en el capítulo 2 se describe la primera de las dos metodologías desarrolladas durante esta tesis doctoral. Así, esta metodología se basa en un proceso tipo DYKAT, combinado con la reacción de Buchwald-Hartwig, usando heterobiarilos electrófilos racémicos y configuracionalmente estables. Así, este protocolo ha podido aplicarse para la síntesis de aminas tipo IAN con altos rendimientos y de buenas a excelentes enantioselectividades. En el capítulo 3, se emplea otra aproximación para la síntesis de heterobiarilos. En este caso, sustratos configuracionalmente lábiles fueron desimetrizados a través de una hidroarilación C-H catalizada por Ir(I). Así, esta aproximación permite la síntesis de heterobiarilos con quiralidad axial y central con alta regio-, diastereo- y enantioselectividades. https://hdl.handle.net/11441/93380 |
| spellingShingle | DYKAT and desymmetrization strategies for the synthesis of axially chiral heterobiaryls Romero Arenas, Antonio |
| status_str | publishedVersion |
| title | DYKAT and desymmetrization strategies for the synthesis of axially chiral heterobiaryls |
| title_full | DYKAT and desymmetrization strategies for the synthesis of axially chiral heterobiaryls |
| title_fullStr | DYKAT and desymmetrization strategies for the synthesis of axially chiral heterobiaryls |
| title_full_unstemmed | DYKAT and desymmetrization strategies for the synthesis of axially chiral heterobiaryls |
| title_short | DYKAT and desymmetrization strategies for the synthesis of axially chiral heterobiaryls |
| title_sort | DYKAT and desymmetrization strategies for the synthesis of axially chiral heterobiaryls |
| url | https://hdl.handle.net/11441/93380 |