Hispana. Acceso en línea al Patrimonio Cultural Digital Español

Está en:  › Dades de registre

δ-Amination of alkyl alcohols via energy transfer photocatalysis

Identificadores del recurso

Organic Chemistry Frontiers 11.24 (2024): 7037-7043

2052-4129 (online)

http://hdl.handle.net/10486/716920

10.1039/D4QO01522C

7037

7043

Procedència

(Biblos-e Archivo)

Fitxa

Títol:: δ-Amination of alkyl alcohols via energy transfer photocatalysis
Tema:: Amination; Amines; Carboxylation; Photocatalytic Activity; Química
Descripció:: Amino alcohols play a crucial role in the realm of biologically active compounds due to their functional diversity. In this study, we introduce a metal-free energy transfer photocatalytic method for the preparation of 1,4-aminoalcohols from readily available alcohol feedstocks. The key feature of this transformation is the simultaneous generation of a persistent iminyl radical and a transient carbon-centered radical through σ-homolytic cleavage of the O–N bond via energy transfer (EnT). The process involves fragmentation/decarboxylation/1,5-HAT (hydrogen atom transfer), leading to the formation of a C(sp3)-hybridized radical, which undergoes selective radical–radical cross-coupling or a radical chain event to yield the desired products. In addition, the protocol was also found to be suitable for N-tosyl amines, giving rise to 1,4-diamines. Our approach combines experimental mechanistic investigations with detailed computational studies using density functional theory (DFT) to provide insights into the reaction mechanism. This innovative method provides a new approach for preparing δ-amino alkyl alcohols and amines; We thank Ministerio de Ciencia, Innovación y Universidades-Agencia Estatal de Investigación (Grants PID2023146801NB-C32, PID2021-1248553NB-100 and PID2020113059GB-C22), the European Union’s Horizon 2020 Research and Innovation programme under Grant agreement N° 101034324 and Comunidad de Madrid (S2022/BMD-7403 RENIM−CM) for financial support
Idioma:: English
Relació:: Gobierno de España. PID2023-146801NB-C32; Gobierno de España. PID2020-113059GB-C22; info:eu-repo/grantAgreement/EC/HE/101034324/EU//CIVIS3i; Comunidad de Madrid. S2022/BMD-7403/RENIM−CM
Autor/Productor:: Cristóbal Gordo, Christian; Alonso Montero, María Inés; Tato, Francisco; Cabrera Afonso, María Jesús; Adrio Sevilla, Francisco Javier; Ribagorda Lobera, María
Editor:: Royal Society of Chemistry
Otros colaboradores/productores:: UAM. Departamento de Química Orgánica
Drets:: http://creativecommons.org/licenses/by-nc/4.0/; open access
Data:: 2024-10-10
Tipo de recurso:: journal article; info:eu-repo/semantics/publishedVersion
Format:: application/pdf

oai_dc

Descarregar XML

<?xml version="1.0" encoding="UTF-8" ?>

<oai_dc:dc schemaLocation="http://www.openarchives.org/OAI/2.0/oai_dc/ http://www.openarchives.org/OAI/2.0/oai_dc.xsd">
1. <dc:title>δ-Amination of alkyl alcohols via energy transfer photocatalysis</dc:title>
2. <dc:creator>Cristóbal Gordo, Christian</dc:creator>
3. <dc:creator>Alonso Montero, María Inés</dc:creator>
4. <dc:creator>Tato, Francisco</dc:creator>
5. <dc:creator>Cabrera Afonso, María Jesús</dc:creator>
6. <dc:creator>Adrio Sevilla, Francisco Javier</dc:creator>
7. <dc:creator>Ribagorda Lobera, María</dc:creator>
8. <dc:contributor>UAM. Departamento de Química Orgánica</dc:contributor>
9. <dc:subject>Amination</dc:subject>
10. <dc:subject>Amines</dc:subject>
11. <dc:subject>Carboxylation</dc:subject>
12. <dc:subject>Photocatalytic Activity</dc:subject>
13. <dc:subject>Química</dc:subject>
14. <dc:description>Amino alcohols play a crucial role in the realm of biologically active compounds due to their functional diversity. In this study, we introduce a metal-free energy transfer photocatalytic method for the preparation of 1,4-aminoalcohols from readily available alcohol feedstocks. The key feature of this transformation is the simultaneous generation of a persistent iminyl radical and a transient carbon-centered radical through σ-homolytic cleavage of the O–N bond via energy transfer (EnT). The process involves fragmentation/decarboxylation/1,5-HAT (hydrogen atom transfer), leading to the formation of a C(sp3)-hybridized radical, which undergoes selective radical–radical cross-coupling or a radical chain event to yield the desired products. In addition, the protocol was also found to be suitable for N-tosyl amines, giving rise to 1,4-diamines. Our approach combines experimental mechanistic investigations with detailed computational studies using density functional theory (DFT) to provide insights into the reaction mechanism. This innovative method provides a new approach for preparing δ-amino alkyl alcohols and amines</dc:description>
15. <dc:description>We thank Ministerio de Ciencia, Innovación y Universidades-Agencia Estatal de Investigación (Grants PID2023146801NB-C32, PID2021-1248553NB-100 and PID2020113059GB-C22), the European Union’s Horizon 2020 Research and Innovation programme under Grant agreement N° 101034324 and Comunidad de Madrid (S2022/BMD-7403 RENIM−CM) for financial support</dc:description>
16. <dc:date>2024-10-10</dc:date>
17. <dc:type>journal article</dc:type>
18. <dc:type>info:eu-repo/semantics/publishedVersion</dc:type>
19. <dc:identifier>Organic Chemistry Frontiers 11.24 (2024): 7037-7043</dc:identifier>
20. <dc:identifier>2052-4129 (online)</dc:identifier>
21. <dc:identifier>http://hdl.handle.net/10486/716920</dc:identifier>
22. <dc:identifier>10.1039/D4QO01522C</dc:identifier>
23. <dc:identifier>7037</dc:identifier>
24. <dc:identifier>24</dc:identifier>
25. <dc:identifier>7043</dc:identifier>
26. <dc:identifier>11</dc:identifier>
27. <dc:language>eng</dc:language>
28. <dc:relation>Gobierno de España. PID2023-146801NB-C32</dc:relation>
29. <dc:relation>Gobierno de España. PID2020-113059GB-C22</dc:relation>
30. <dc:relation>info:eu-repo/grantAgreement/EC/HE/101034324/EU//CIVIS3i</dc:relation>
31. <dc:relation>Comunidad de Madrid. S2022/BMD-7403/RENIM−CM</dc:relation>
32. <dc:rights>http://creativecommons.org/licenses/by-nc/4.0/</dc:rights>
33. <dc:rights>open access</dc:rights>
34. <dc:format>application/pdf</dc:format>
35. <dc:publisher>Royal Society of Chemistry</dc:publisher>
</oai_dc:dc>

oai_openaire

Descarregar XML

<?xml version="1.0" encoding="UTF-8" ?>

<oaire:resource schemaLocation="http://namespace.openaire.eu/schema/oaire/ https://www.openaire.eu/schema/repo-lit/4.0/openaire.xsd">
1. <datacite:titles>
  1. <datacite:title>δ-Amination of alkyl alcohols via energy transfer photocatalysis</datacite:title>
  </datacite:titles>
2. <datacite:creators>
  1. <datacite:creator>
    1. <datacite:creatorName>Cristóbal Gordo, Christian</datacite:creatorName>
    </datacite:creator>
  2. <datacite:creator>
    1. <datacite:creatorName>Alonso Montero, María Inés</datacite:creatorName>
    2. <datacite:nameIdentifier nameIdentifierScheme="ORCID" schemeURI="https://orcid.org">0000-0002-5556-5995</datacite:nameIdentifier>
    3. <datacite:affiliation>Universidad Autónoma de Madrid</datacite:affiliation>
    </datacite:creator>
  3. <datacite:creator>
    1. <datacite:creatorName>Tato, Francisco</datacite:creatorName>
    </datacite:creator>
  4. <datacite:creator>
    1. <datacite:creatorName>Cabrera Afonso, María Jesús</datacite:creatorName>
    </datacite:creator>
  5. <datacite:creator>
    1. <datacite:creatorName>Adrio Sevilla, Francisco Javier</datacite:creatorName>
    2. <datacite:nameIdentifier nameIdentifierScheme="ORCID" schemeURI="https://orcid.org">0000-0001-6238-6533</datacite:nameIdentifier>
    3. <datacite:affiliation>Universidad Autónoma de Madrid</datacite:affiliation>
    </datacite:creator>
  6. <datacite:creator>
    1. <datacite:creatorName>Ribagorda Lobera, María</datacite:creatorName>
    2. <datacite:nameIdentifier nameIdentifierScheme="ORCID" schemeURI="https://orcid.org">0000-0001-7185-4095</datacite:nameIdentifier>
    3. <datacite:affiliation>Universidad Autónoma de Madrid</datacite:affiliation>
    </datacite:creator>
  </datacite:creators>
3. <datacite:contributors>
  1. <datacite:contributor contributorType="Other">
    1. <datacite:contributorName>UAM. Departamento de Química Orgánica</datacite:contributorName>
    </datacite:contributor>
  </datacite:contributors>
4. <datacite:subjects>
  1. <datacite:subject>Amination</datacite:subject>
  2. <datacite:subject>Amines</datacite:subject>
  3. <datacite:subject>Carboxylation</datacite:subject>
  4. <datacite:subject>Photocatalytic Activity</datacite:subject>
  5. <datacite:subject>Química</datacite:subject>
  </datacite:subjects>
5. <dc:description>Amino alcohols play a crucial role in the realm of biologically active compounds due to their functional diversity. In this study, we introduce a metal-free energy transfer photocatalytic method for the preparation of 1,4-aminoalcohols from readily available alcohol feedstocks. The key feature of this transformation is the simultaneous generation of a persistent iminyl radical and a transient carbon-centered radical through σ-homolytic cleavage of the O–N bond via energy transfer (EnT). The process involves fragmentation/decarboxylation/1,5-HAT (hydrogen atom transfer), leading to the formation of a C(sp3)-hybridized radical, which undergoes selective radical–radical cross-coupling or a radical chain event to yield the desired products. In addition, the protocol was also found to be suitable for N-tosyl amines, giving rise to 1,4-diamines. Our approach combines experimental mechanistic investigations with detailed computational studies using density functional theory (DFT) to provide insights into the reaction mechanism. This innovative method provides a new approach for preparing δ-amino alkyl alcohols and amines</dc:description>
6. <dc:description>We thank Ministerio de Ciencia, Innovación y Universidades-Agencia Estatal de Investigación (Grants PID2023146801NB-C32, PID2021-1248553NB-100 and PID2020113059GB-C22), the European Union’s Horizon 2020 Research and Innovation programme under Grant agreement N° 101034324 and Comunidad de Madrid (S2022/BMD-7403 RENIM−CM) for financial support</dc:description>
7. <datacite:dates>
  1. <datacite:date dateType="Issued">2024-10-10</datacite:date>
  </datacite:dates>
8. <oaire:resourceType resourceTypeGeneral="literature" uri="http://purl.org/coar/resource_type/c_6501">journal article</oaire:resourceType>
9. <oaire:version uri="http://purl.org/coar/version/c_be7fb7dd8ff6fe43">NA</oaire:version>
10. <datacite:identifier identifierType="HANDLE">http://hdl.handle.net/10486/716920</datacite:identifier>
11. <datacite:alternateIdentifiers>
  1. <datacite:alternateIdentifier alternateIdentifierType="DOI">10.1039/D4QO01522C</datacite:alternateIdentifier>
  </datacite:alternateIdentifiers>
12. <datacite:relatedIdentifiers>
  1. <datacite:relatedIdentifier relatedIdentifierType="ISSN" relationType="IsPartOf">2052-4129 (online)</datacite:relatedIdentifier>
  </datacite:relatedIdentifiers>
13. <dc:language>eng</dc:language>
14. <datacite:rights rightsURI="http://purl.org/coar/access_right/c_abf2">open access</datacite:rights>
15. <oaire:licenseCondition uri="http://creativecommons.org/licenses/by-nc/4.0/">Attribution-NonCommercial 4.0 International</oaire:licenseCondition>
16. <dc:format>application/pdf</dc:format>
17. <datacite:sizes>
  1. <datacite:size>7 pag.</datacite:size>
  </datacite:sizes>
18. <dc:publisher>Royal Society of Chemistry</dc:publisher>
19. <oaire:file objectType="fulltext">https://repositorio.uam.es/bitstream/10486/716920/1/amination_cristobal_OCF_2024.pdf</oaire:file>
</oaire:resource>

xoai

Descarregar XML

<?xml version="1.0" encoding="UTF-8" ?>

<metadata schemaLocation="http://www.lyncode.com/xoai http://www.lyncode.com/xsd/xoai.xsd">
1. <element name="dc">
  1. <element name="contributor">
    1. <element name="author">
      1. <element name="none">
        <field name="value">Cristóbal Gordo, Christian</field>
        <field name="authority">048ff47e-6967-4882-ba34-8a9dcfe91fe5</field>
        <field name="confidence">600</field>
        <field name="orcid_id" />
        <field name="value">Alonso Montero, María Inés</field>
        <field name="authority">259484</field>
        <field name="confidence">600</field>
        <field name="orcid_id">0000-0002-5556-5995</field>
        <field name="value">Tato, Francisco</field>
        <field name="authority">95ed06cc-a507-457c-8cb7-1d2bd5e0b3c8</field>
        <field name="confidence">600</field>
        <field name="orcid_id" />
        <field name="value">Cabrera Afonso, María Jesús</field>
        <field name="authority">b5968f79-5259-4a4f-bb3c-7077722766b6</field>
        <field name="confidence">600</field>
        <field name="orcid_id" />
        <field name="value">Adrio Sevilla, Francisco Javier</field>
        <field name="authority">261106</field>
        <field name="confidence">600</field>
        <field name="orcid_id">0000-0001-6238-6533</field>
        <field name="value">Ribagorda Lobera, María</field>
        <field name="authority">258884</field>
        <field name="confidence">600</field>
        <field name="orcid_id">0000-0001-7185-4095</field>
        </element>
      </element>
    2. <element name="other">
      1. <element name="es_ES">
        <field name="value">UAM. Departamento de Química Orgánica</field>
        </element>
      </element>
    </element>
  2. <element name="date">
    1. <element name="issued">
      1. <element name="none">
        <field name="value">2024-10-10</field>
        </element>
      </element>
    </element>
  3. <element name="identifier">
    1. <element name="citation">
      1. <element name="es_ES">
        <field name="value">Organic Chemistry Frontiers 11.24 (2024): 7037-7043</field>
        </element>
      </element>
    2. <element name="issn">
      1. <element name="es_ES">
        <field name="value">2052-4129 (online)</field>
        </element>
      </element>
    3. <element name="uri">
      1. <element name="none">
        <field name="value">http://hdl.handle.net/10486/716920</field>
        </element>
      </element>
    4. <element name="doi">
      1. <element name="es_ES">
        <field name="value">10.1039/D4QO01522C</field>
        </element>
      </element>
    5. <element name="publicationfirstpage">
      1. <element name="es_ES">
        <field name="value">7037</field>
        </element>
      </element>
    6. <element name="publicationissue">
      1. <element name="es_ES">
        <field name="value">24</field>
        </element>
      </element>
    7. <element name="publicationlastpage">
      1. <element name="es_ES">
        <field name="value">7043</field>
        </element>
      </element>
    8. <element name="publicationvolume">
      1. <element name="es_ES">
        <field name="value">11</field>
        </element>
      </element>
    </element>
  4. <element name="description">
    1. <element name="abstract">
      1. <element name="es_ES">
        <field name="value">Amino alcohols play a crucial role in the realm of biologically active compounds due to their functional diversity. In this study, we introduce a metal-free energy transfer photocatalytic method for the preparation of 1,4-aminoalcohols from readily available alcohol feedstocks. The key feature of this transformation is the simultaneous generation of a persistent iminyl radical and a transient carbon-centered radical through σ-homolytic cleavage of the O–N bond via energy transfer (EnT). The process involves fragmentation/decarboxylation/1,5-HAT (hydrogen atom transfer), leading to the formation of a C(sp3)-hybridized radical, which undergoes selective radical–radical cross-coupling or a radical chain event to yield the desired products. In addition, the protocol was also found to be suitable for N-tosyl amines, giving rise to 1,4-diamines. Our approach combines experimental mechanistic investigations with detailed computational studies using density functional theory (DFT) to provide insights into the reaction mechanism. This innovative method provides a new approach for preparing δ-amino alkyl alcohols and amines</field>
        </element>
      </element>
    2. <element name="sponsorship">
      1. <element name="es_ES">
        <field name="value">We thank Ministerio de Ciencia, Innovación y Universidades-Agencia Estatal de Investigación (Grants PID2023146801NB-C32, PID2021-1248553NB-100 and PID2020113059GB-C22), the European Union’s Horizon 2020 Research and Innovation programme under Grant agreement N° 101034324 and Comunidad de Madrid (S2022/BMD-7403 RENIM−CM) for financial support</field>
        </element>
      </element>
    </element>
  5. <element name="format">
    1. <element name="extent">
      1. <element name="es_ES">
        <field name="value">7 pag.</field>
        </element>
      </element>
    2. <element name="mimetype">
      1. <element name="es_ES">
        <field name="value">application/pdf</field>
        </element>
      </element>
    </element>
  6. <element name="language">
    1. <element name="iso">
      1. <element name="es_ES">
        <field name="value">eng</field>
        </element>
      </element>
    </element>
  7. <element name="publisher">
    1. <element name="es_ES">
      1. <field name="value">Royal Society of Chemistry</field>
      </element>
    </element>
  8. <element name="relation">
    1. <element name="projectID">
      1. <element name="es_ES">
        <field name="value">Gobierno de España. PID2023-146801NB-C32</field>
        <field name="value">Gobierno de España. PID2020-113059GB-C22</field>
        <field name="value">info:eu-repo/grantAgreement/EC/HE/101034324/EU//CIVIS3i</field>
        <field name="value">Comunidad de Madrid. S2022/BMD-7403/RENIM−CM</field>
        </element>
      </element>
    </element>
  9. <element name="rights">
    1. <element name="uri">
      1. <element name="es_ES">
        <field name="value">http://creativecommons.org/licenses/by-nc/4.0/</field>
        </element>
      </element>
    2. <element name="accessRights">
      1. <element name="es_ES">
        <field name="value">open access</field>
        </element>
      </element>
    </element>
  10. <element name="subject">
    1. <element name="other">
      1. <element name="en_US">
        <field name="value">Amination</field>
        <field name="value">Amines</field>
        <field name="value">Carboxylation</field>
        <field name="value">Photocatalytic Activity</field>
        </element>
      </element>
    2. <element name="eciencia">
      1. <element name="es_ES">
        <field name="value">Química</field>
        </element>
      </element>
    </element>
  11. <element name="title">
    1. <element name="es_ES">
      1. <field name="value">δ-Amination of alkyl alcohols via energy transfer photocatalysis</field>
      </element>
    </element>
  12. <element name="type">
    1. <element name="es_ES">
      1. <field name="value">journal article</field>
      </element>
    2. <element name="version">
      1. <element name="es_ES">
        <field name="value">info:eu-repo/semantics/publishedVersion</field>
        </element>
      </element>
    </element>
  13. <element name="facultadUAM">
    1. <element name="es_ES">
      1. <field name="value">Facultad de Ciencias</field>
      </element>
    </element>
  14. <element name="institutoUAM">
    1. <element name="es_ES">
      1. <field name="value">Instituto de Investigación Avanzada en Ciencias Químicas (IAdChem)</field>
      </element>
    </element>
  15. <element name="apcUAM">
    1. <element name="es_ES">
      1. <field name="value">APC financiada por la UAM. RSC</field>
      </element>
    </element>
  </element>
2. <element name="bundles">
  1. <element name="bundle">
    1. <field name="name">LICENSE</field>
    2. <element name="bitstreams">
      1. <element name="bitstream">
        <field name="name">license.txt</field>
        <field name="originalName">license.txt</field>
        <field name="format">text/plain; charset=utf-8</field>
        <field name="size">4105</field>
        <field name="url">https://repositorio.uam.es/bitstream/10486/716920/2/license.txt</field>
        <field name="checksum">c9c6ba57a9a0757a94b73bd12b549d9f</field>
        <field name="checksumAlgorithm">MD5</field>
        <field name="sid">2</field>
        </element>
      </element>
    </element>
  2. <element name="bundle">
    1. <field name="name">ORIGINAL</field>
    2. <element name="bitstreams">
      1. <element name="bitstream">
        <field name="name">amination_cristobal_OCF_2024.pdf</field>
        <field name="originalName">amination_cristobal_OCF_2024.pdf</field>
        <field name="format">application/pdf</field>
        <field name="size">1368748</field>
        <field name="url">https://repositorio.uam.es/bitstream/10486/716920/1/amination_cristobal_OCF_2024.pdf</field>
        <field name="checksum">c00955c17cf2a2a2cd92ebf1e9a4ccd2</field>
        <field name="checksumAlgorithm">MD5</field>
        <field name="sid">1</field>
        </element>
      </element>
    </element>
  3. <element name="bundle">
    1. <field name="name">THUMBNAIL</field>
    2. <element name="bitstreams">
      1. <element name="bitstream">
        <field name="name">amination_cristobal_OCF_2024.pdf.jpg</field>
        <field name="originalName">amination_cristobal_OCF_2024.pdf.jpg</field>
        <field name="description">IM Thumbnail</field>
        <field name="format">image/jpeg</field>
        <field name="size">4376</field>
        <field name="url">https://repositorio.uam.es/bitstream/10486/716920/3/amination_cristobal_OCF_2024.pdf.jpg</field>
        <field name="checksum">bfd91ee62e104cc74a2df1949293da5b</field>
        <field name="checksumAlgorithm">MD5</field>
        <field name="sid">3</field>
        </element>
      </element>
    </element>
  4. <element name="bundle">
    1. <field name="name">TEXT</field>
    2. <element name="bitstreams">
      1. <element name="bitstream">
        <field name="name">amination_cristobal_OCF_2024.pdf.txt</field>
        <field name="originalName">amination_cristobal_OCF_2024.pdf.txt</field>
        <field name="description">Extracted text</field>
        <field name="format">text/plain</field>
        <field name="size">27561</field>
        <field name="url">https://repositorio.uam.es/bitstream/10486/716920/4/amination_cristobal_OCF_2024.pdf.txt</field>
        <field name="checksum">208c2d59d92eba48123289aa284dea8b</field>
        <field name="checksumAlgorithm">MD5</field>
        <field name="sid">4</field>
        </element>
      </element>
    </element>
  </element>
3. <element name="others">
  1. <field name="handle">10486/716920</field>
  2. <field name="identifier">oai:repositorio.uam.es:10486/716920</field>
  3. <field name="lastModifyDate">2025-04-08 12:59:50.275</field>
  </element>
4. <element name="repository">
  1. <field name="name">Universidad Autónoma de Madrid</field>
  2. <field name="mail">biblosearchivo.biblioteca@uam.es</field>
  </element>
5. <element name="license">
  1. <field name="bin">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</field>
  </element>
</metadata>