Repository logo
 
Publication

Photochemical reactions of acylsilanes towards the construction of carbon-carbon bonds

2023-03Doctoral thesis Open access
Simple item page
datacite.subject.fosCiências Médicas::Medicina Básicapt_PT
dc.contributor.advisorCandeias, Nuno Filipe Rafael
dc.contributor.advisorAfonso, Carlos Alberto Mateus
dc.contributor.authorVale, João R.
dc.date.accessioned2024-06-03T09:00:42Z
dc.date.available2024-06-03T09:00:42Z
dc.date.issued2023-03
dc.date.submitted2023-10
dc.description.abstractPhotochemistry is a field of chemistry which has fascinated chemists for centuries. The access to the photoexcited state of molecules allows otherwise unattainable reactivity and access to completely novel structures. The use of light as a reagent in organic synthesis can also circumvent the need of toxic or expensive reagents commonly used in traditional synthetic chemistry, making photochemistry an attractive tool in the context of Green Chemistry. Acylsilanes are a class of compounds with rich photochemistry. They possess the unique ability to undergo photorearrangement to reactive nucleophilic siloxycarbenes. While this metal-free method for carbene generation is highly promising, the number of known efficient reactions they undergo is limited and underexplored. In this thesis, a variety of acylsilanes have been synthesized in order to further explore and expand their known photo reactivity and obtain new complex structures via C-C bound forming photoreactions. A regioselective intramolecular [2+2]-photocycloaddition of benzoyl(allyl)silanes was developed to yield novel silacyclopentanes, compounds that may be used as silicon bioisosteres of cyclopentanes. Additionally, a novel formal (4+1)-cycloaddition of photogenerated siloxycarbene with electrophilic dienes was discovered, allowing the synthesis of highly functionalized cyclopentenes and expanding the limited reactivity of such carbenes with olefins. During the synthesis of acylsilanes via the dithiane umpolung methodology an autooxidative condensation of lithiated aryl dithianes was serendipitously uncovered, which yielded complex α-thioether ketone orthothioesters, some of which present strong cytotoxic activity against glioblastoma cancer cell lines.pt_PT
dc.description.provenanceSubmitted by Paula Guerreiro (passarinho@reitoria.ulisboa.pt) on 2024-05-24T15:05:21Z No. of bitstreams: 1 scnd990026354741672_td_João_Vale.pdf: 11362898 bytes, checksum: 1f4b0ed7deb3a141f80063fe357e1db9 (MD5)en
dc.description.provenanceMade available in DSpace on 2024-06-03T09:00:42Z (GMT). No. of bitstreams: 1 scnd990026354741672_td_João_Vale.pdf: 11362898 bytes, checksum: 1f4b0ed7deb3a141f80063fe357e1db9 (MD5) Previous issue date: 2023-03en
dc.identifier.tid101592469pt_PT
dc.identifier.urihttp://hdl.handle.net/10451/64951
dc.language.isoengpt_PT
dc.relationSynthetic valorization of furan based building blocks derived from renewable resources
dc.subjectFotoquímicapt_PT
dc.subjectAcilsilanospt_PT
dc.subjectCarbenospt_PT
dc.subjectCiclopentanospt_PT
dc.subjectPhotochemistrypt_PT
dc.subjectAcylsilanespt_PT
dc.subjectCarbenept_PT
dc.subjectMetal-freept_PT
dc.subjectCyclopentanespt_PT
dc.titlePhotochemical reactions of acylsilanes towards the construction of carbon-carbon bondspt_PT
dc.typedoctoral thesis
dspace.entity.typePublication
oaire.awardTitleSynthetic valorization of furan based building blocks derived from renewable resources
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/OE/SFRH%2FBD%2F120119%2F2016/PT
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/Concurso para Financiamento de Projetos de Investigação Científica e Desenvolvimento Tecnológico em Todos os Domínios Científicos - 2017/PTDC%2FQUI-QOR%2F32008%2F2017/PT
oaire.fundingStreamOE
oaire.fundingStreamConcurso para Financiamento de Projetos de Investigação Científica e Desenvolvimento Tecnológico em Todos os Domínios Científicos - 2017
person.familyNameVale
person.givenNameJoão
person.identifier.ciencia-idDF1D-6E5E-9EE7
person.identifier.orcid0000-0003-0411-9618
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.nameFundação para a Ciência e a Tecnologia
project.funder.nameFundação para a Ciência e a Tecnologia
rcaap.rightsopenAccesspt_PT
rcaap.typedoctoralThesispt_PT
relation.isAuthorOfPublication70df5545-6eb8-4c2b-ab3b-e10a2ab6ad69
relation.isAuthorOfPublication.latestForDiscovery70df5545-6eb8-4c2b-ab3b-e10a2ab6ad69
relation.isProjectOfPublication17a17a63-e846-4bcb-bd4e-0d45936f44e7
relation.isProjectOfPublicationcf938497-364d-4e26-b999-147b55961060
relation.isProjectOfPublication.latestForDiscoverycf938497-364d-4e26-b999-147b55961060
thesis.degree.nameTese de doutoramento, Farmácia (Química Farmacêutica e Terapêutica), Universidade de Lisboa, Faculdade de Farmácia, 2023pt_PT

Files

Original bundle
Now showing 1 - 1 of 1
No Thumbnail Available
Name:
scnd990026354741672_td_João_Vale.pdf
Size:
10.84 MB
Format:
Adobe Portable Document Format
Download
License bundle
Now showing 1 - 1 of 1
No Thumbnail Available
Name:
license.txt
Size:
1.2 KB
Format:
Item-specific license agreed upon to submission
Description:
Download

Collections