Stereoselective, ruthenium-photocatalyzed synthesis of 1,2-diaminotruxinic bis-amino acids from 4-arylidene-5(4 H)-oxazolones

The irradiation of (Z)-2-phenyl-4-aryliden-5(4H)-oxazolones 1 in deoxygenated CH2Cl2 at 25 °C with blue light (465 nm) in the presence of [Ru(bpy)3](BF4)2 (5% mole ratio) as a triplet photocatalyst promotes the [2+2] photocycloaddition of the C═C bonds of the 4-arylidene moiety, thus allowing the co...

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Autores: Sierra, Sonia, Gómez, M. Victoria, Jiménez, Ana I., Pop, Alexandra, Silvestru, Cristian, Marín, María Luisa, Boscá, Francisco, Sastre, Germán, Gómez-Bengoa, Enrique, Urriolabeitia, Esteban P.
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2022
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/272493
Acesso em linha:http://hdl.handle.net/10261/272493
Access Level:acceso abierto
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oai_identifier_str oai:digital.csic.es:10261/272493
network_acronym_str ES
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repository_id_str
dc.title.none.fl_str_mv Stereoselective, ruthenium-photocatalyzed synthesis of 1,2-diaminotruxinic bis-amino acids from 4-arylidene-5(4 H)-oxazolones
title Stereoselective, ruthenium-photocatalyzed synthesis of 1,2-diaminotruxinic bis-amino acids from 4-arylidene-5(4 H)-oxazolones
spellingShingle Stereoselective, ruthenium-photocatalyzed synthesis of 1,2-diaminotruxinic bis-amino acids from 4-arylidene-5(4 H)-oxazolones
Sierra, Sonia
title_short Stereoselective, ruthenium-photocatalyzed synthesis of 1,2-diaminotruxinic bis-amino acids from 4-arylidene-5(4 H)-oxazolones
title_full Stereoselective, ruthenium-photocatalyzed synthesis of 1,2-diaminotruxinic bis-amino acids from 4-arylidene-5(4 H)-oxazolones
title_fullStr Stereoselective, ruthenium-photocatalyzed synthesis of 1,2-diaminotruxinic bis-amino acids from 4-arylidene-5(4 H)-oxazolones
title_full_unstemmed Stereoselective, ruthenium-photocatalyzed synthesis of 1,2-diaminotruxinic bis-amino acids from 4-arylidene-5(4 H)-oxazolones
title_sort Stereoselective, ruthenium-photocatalyzed synthesis of 1,2-diaminotruxinic bis-amino acids from 4-arylidene-5(4 H)-oxazolones
dc.creator.none.fl_str_mv Sierra, Sonia
Gómez, M. Victoria
Jiménez, Ana I.
Pop, Alexandra
Silvestru, Cristian
Marín, María Luisa
Boscá, Francisco
Sastre, Germán
Gómez-Bengoa, Enrique
Urriolabeitia, Esteban P.
author Sierra, Sonia
author_facet Sierra, Sonia
Gómez, M. Victoria
Jiménez, Ana I.
Pop, Alexandra
Silvestru, Cristian
Marín, María Luisa
Boscá, Francisco
Sastre, Germán
Gómez-Bengoa, Enrique
Urriolabeitia, Esteban P.
author_role author
author2 Gómez, M. Victoria
Jiménez, Ana I.
Pop, Alexandra
Silvestru, Cristian
Marín, María Luisa
Boscá, Francisco
Sastre, Germán
Gómez-Bengoa, Enrique
Urriolabeitia, Esteban P.
author2_role author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia, Innovación y Universidades (España)
Agencia Estatal de Investigación (España)
European Commission
Gobierno de Aragón
Consejo Superior de Investigaciones Científicas (España)
Universidad Politécnica de Valencia
Universidad del País Vasco
Ministry of Education and Scientific Research (Romania)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description The irradiation of (Z)-2-phenyl-4-aryliden-5(4H)-oxazolones 1 in deoxygenated CH2Cl2 at 25 °C with blue light (465 nm) in the presence of [Ru(bpy)3](BF4)2 (5% mole ratio) as a triplet photocatalyst promotes the [2+2] photocycloaddition of the C═C bonds of the 4-arylidene moiety, thus allowing the completely regio- and stereoselective formation of cyclobutane-bis(oxazolone)s 2 as single stereoisomers. Cyclobutanes 2 have been unambiguously characterized as the μ-isomers and contain two E-oxazolones coupled in an anti-head-to-head form. The use of continuous-flow techniques in microreactors allows the synthesis of cyclobutanes 2 in only 60 min, compared with the 24–48 h required in batch mode. Ring opening of the oxazolone heterocycle in 2 with a base affords the corresponding 1,2-diaminotruxinic bis-amino esters 3, which are also obtained selectively as μ-isomers. The ruthenium complex behaves as a triplet photocatalyst, generating the reactive excited state of the oxazolone via an energy-transfer process. This reactive excited state has been characterized as a triplet diradical 3(E/Z)-1* by laser flash photolysis (transient absorption spectroscopy). This technique also shows that this excited state is the same when starting from either (Z)- or (E)-oxazolones. Density functional theory calculations show that the first step of the [2+2] cycloaddition between 3(E/Z)-1* and (Z)-1 is formation of the C(H)–C(H) bond and that (Z) to (E) isomerization takes place at the 1,4-diradical thus formed.
publishDate 2022
dc.date.none.fl_str_mv 2022
2022
2022
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
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info:eu-repo/semantics/publishedVersion
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dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/272493
url http://hdl.handle.net/10261/272493
dc.language.none.fl_str_mv Inglés
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dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
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dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
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instname_str Consejo Superior de Investigaciones Científicas (CSIC)
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spelling Stereoselective, ruthenium-photocatalyzed synthesis of 1,2-diaminotruxinic bis-amino acids from 4-arylidene-5(4 H)-oxazolonesSierra, SoniaGómez, M. VictoriaJiménez, Ana I.Pop, AlexandraSilvestru, CristianMarín, María LuisaBoscá, FranciscoSastre, GermánGómez-Bengoa, EnriqueUrriolabeitia, Esteban P.The irradiation of (Z)-2-phenyl-4-aryliden-5(4H)-oxazolones 1 in deoxygenated CH2Cl2 at 25 °C with blue light (465 nm) in the presence of [Ru(bpy)3](BF4)2 (5% mole ratio) as a triplet photocatalyst promotes the [2+2] photocycloaddition of the C═C bonds of the 4-arylidene moiety, thus allowing the completely regio- and stereoselective formation of cyclobutane-bis(oxazolone)s 2 as single stereoisomers. Cyclobutanes 2 have been unambiguously characterized as the μ-isomers and contain two E-oxazolones coupled in an anti-head-to-head form. The use of continuous-flow techniques in microreactors allows the synthesis of cyclobutanes 2 in only 60 min, compared with the 24–48 h required in batch mode. Ring opening of the oxazolone heterocycle in 2 with a base affords the corresponding 1,2-diaminotruxinic bis-amino esters 3, which are also obtained selectively as μ-isomers. The ruthenium complex behaves as a triplet photocatalyst, generating the reactive excited state of the oxazolone via an energy-transfer process. This reactive excited state has been characterized as a triplet diradical 3(E/Z)-1* by laser flash photolysis (transient absorption spectroscopy). This technique also shows that this excited state is the same when starting from either (Z)- or (E)-oxazolones. Density functional theory calculations show that the first step of the [2+2] cycloaddition between 3(E/Z)-1* and (Z)-1 is formation of the C(H)–C(H) bond and that (Z) to (E) isomerization takes place at the 1,4-diradical thus formed.The authors thank the Spanish Government for funding: Project PID2020-119636GB-I00, funded by MCIN/AEI/10.13039/501100011033; Projects PID2019-106394GB-I00/AEI/10.13039/501100011033, PID2019-110441RB-C33/AEI/10.13039/501100011033, and PID2019-110008GB-I00/AEI/10.13039/501100011033, funded by MCIN/AEI/10.13039/501100011033; Projects RTI2018-101784-B-I00, RTI2018-101033-B-I00, and CTQ2017-84825-R, funded by MCIN/AEI/10.13039/501100011033 and FEDER Una manera de hacer Europa. E.P.U., A.I.J., and S.S. thank Gobierno de Aragón-FSE (Spain, research group Aminoácidos y Péptidos E19_20R) for funding. G.S. thanks CTI-CSIC and ASIC-UPV for the use of computational facilities. E.G.-B. thanks SGIker (UPV/EHU) for providing human and computational resources. A.P. is grateful for the financial support of the Romanian Ministry of Education and Research through Grant PN-III-P1-1.1-MC-2018-2580. S.S. thanks Gobierno de Aragón-FSE for a Ph.D. fellowship.Peer reviewedAmerican Chemical SocietyMinisterio de Ciencia, Innovación y Universidades (España)Agencia Estatal de Investigación (España)European CommissionGobierno de AragónConsejo Superior de Investigaciones Científicas (España)Universidad Politécnica de ValenciaUniversidad del País VascoMinistry of Education and Scientific Research (Romania)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202220222022info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/272493reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-119636GB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-106394GB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-110441RB-C33info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-110008GB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-101784-B-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-101033-B-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-84825-Rhttps://doi.org/10.1021/acs.joc.1c03092Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2724932026-05-22T06:33:51Z
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