Rhodium-catalyzed cyclization reactions of 1,5-bisallenes involving alkenes and alkynes: experimental and theoretical studies

The development of novel catalytic methodologies involving the formation of carbon – carbon/heteroatom bonds to produce cyclic systems constitutes a field of great interest in the modern synthetic organic chemistry. Over the last 30 years, the combined use of transition metals with allenes allowed c...

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Autor: Vila Vadrí, Jordi
Tipo de recurso: tesis doctoral
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:CBUC, CESCA
Repositorio:TDR. Tesis Doctorales en Red
OAI Identifier:oai:www.tdx.cat:10803/688847
Acceso en línea:http://hdl.handle.net/10803/688847
Access Level:acceso abierto
Palabra clave:Catàlisi
Catálisis
Catalysis
Rodi
Rodio
Rhodium
Reaccions de ciclació
Reacciones de ciclación
Cyclization reactions
Al·lens
Alenos
Allenes
Càlculs DFT
Cálculos DFT
DFT calculations
Cicloaddició
Cicloadición
Cycloaddition
547
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oai_identifier_str oai:www.tdx.cat:10803/688847
network_acronym_str ES
network_name_str España
repository_id_str
dc.title.none.fl_str_mv Rhodium-catalyzed cyclization reactions of 1,5-bisallenes involving alkenes and alkynes: experimental and theoretical studies
title Rhodium-catalyzed cyclization reactions of 1,5-bisallenes involving alkenes and alkynes: experimental and theoretical studies
spellingShingle Rhodium-catalyzed cyclization reactions of 1,5-bisallenes involving alkenes and alkynes: experimental and theoretical studies
Vila Vadrí, Jordi
Catàlisi
Catálisis
Catalysis
Rodi
Rodio
Rhodium
Reaccions de ciclació
Reacciones de ciclación
Cyclization reactions
Al·lens
Alenos
Allenes
Càlculs DFT
Cálculos DFT
DFT calculations
Cicloaddició
Cicloadición
Cycloaddition
547
title_short Rhodium-catalyzed cyclization reactions of 1,5-bisallenes involving alkenes and alkynes: experimental and theoretical studies
title_full Rhodium-catalyzed cyclization reactions of 1,5-bisallenes involving alkenes and alkynes: experimental and theoretical studies
title_fullStr Rhodium-catalyzed cyclization reactions of 1,5-bisallenes involving alkenes and alkynes: experimental and theoretical studies
title_full_unstemmed Rhodium-catalyzed cyclization reactions of 1,5-bisallenes involving alkenes and alkynes: experimental and theoretical studies
title_sort Rhodium-catalyzed cyclization reactions of 1,5-bisallenes involving alkenes and alkynes: experimental and theoretical studies
dc.creator.none.fl_str_mv Vila Vadrí, Jordi
author Vila Vadrí, Jordi
author_facet Vila Vadrí, Jordi
author_role author
dc.contributor.none.fl_str_mv Roglans i Ribas, Anna
Pla i Quintana, Anna
Universitat de Girona. Departament de Química
Universitat de Girona. Institut de Química Computacional i Catàlisi
dc.subject.none.fl_str_mv Catàlisi
Catálisis
Catalysis
Rodi
Rodio
Rhodium
Reaccions de ciclació
Reacciones de ciclación
Cyclization reactions
Al·lens
Alenos
Allenes
Càlculs DFT
Cálculos DFT
DFT calculations
Cicloaddició
Cicloadición
Cycloaddition
547
topic Catàlisi
Catálisis
Catalysis
Rodi
Rodio
Rhodium
Reaccions de ciclació
Reacciones de ciclación
Cyclization reactions
Al·lens
Alenos
Allenes
Càlculs DFT
Cálculos DFT
DFT calculations
Cicloaddició
Cicloadición
Cycloaddition
547
description The development of novel catalytic methodologies involving the formation of carbon – carbon/heteroatom bonds to produce cyclic systems constitutes a field of great interest in the modern synthetic organic chemistry. Over the last 30 years, the combined use of transition metals with allenes allowed considerable progress in this field. Allenes are cumulated dienes, constituted by two perpendicular double bonds. The unsaturation spread over three contiguous carbons gives allenes additional versatility in cyclization reactions compared to other unsaturations, such as alkenes or alkynes, although the control of the selectivity becomes more challenging when allenes are used. One paradigmatic process to produce cyclic systems is the transition metal-catalyzed [2+2+2] cycloaddition reaction, which enable the simultaneous formation of several bonds and/or stereogenic centers in a single step to produce six-membered rings in perfect atom economy. Our group has developed several rhodium-catalyzed [2+2+2] cycloaddition reactions and has made great mechanistic contributions employing DFT calculations and experimental techniques. Regarding the use of allenes, our group studied the rhodium(I)-catalyzed intramolecular [2+2+2] cycloaddition of linear substrates accommodating allenes and alkynes and/or alkenes. However, [2+2+2] cycloadditions involving two allenes with another unsaturated carbon – carbon bond remain scarce. Considering this, and as part of our continuous interest in the use of allenes, we envisaged the development of partially intramolecular [2+2+2] cycloaddition reactions of 1,5-bisallenes with alkenes and alkynes. Although 1,5-bisallenes exhibited rich chemistry with transition metals, very few examples were reported involving the incorporation of a third unsaturated partner in a cycloaddition reaction. The main goal set within the context of this thesis was to develop new rhodium(I)-catalyzed cycloaddition reactions of 1,5-bisallenes with alkenes and alkynes. As reported in chapter 3, we have succeeded in reacting 1,5-bisallenes with a series of alkenes employing rhodium(I) catalysis. The reaction provided a series of polycyclic dihydroazepine and dihydrooxepine derivatives in a single step and perfect atom economy. The results obtained in chapter 3 allowed us to develop an homodimerization process of 1,5-bisallenes to obtain spirocyclic derivatives featuring six- and seven- membered rings in the spiro carbon (chapter 4). The process was found to be highly chemo- and regioselective, affording a single isomer out of six possible adducts. Moving forward to the use of alkynes, in chapter 5 and 6 we accomplished the proposed objectives by reacting 1,5-bisallenes and alkynes to form cis-3,4-arylvinyl pyrrolidines and cyclopentanes (chapter 5), and bicyclic trans-fused 3,6-dimethylenecyclohex-1-ene derivatives (chapter 6) from 1,5-bisallenes and alkynes using rhodium(I) as a catalyst. Additionally, the mechanism of the reaction was studied in all the developed protocols by means of DFT calculations and experimental techniques that allowed justify the selectivities observed
publishDate 2023
dc.date.none.fl_str_mv 2023
2023
2023
dc.type.none.fl_str_mv info:eu-repo/semantics/doctoralThesis
info:eu-repo/semantics/publishedVersion
format doctoralThesis
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10803/688847
url http://hdl.handle.net/10803/688847
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv http://creativecommons.org/licenses/by-nc/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 237 p.
application/pdf
dc.publisher.none.fl_str_mv Universitat de Girona
publisher.none.fl_str_mv Universitat de Girona
dc.source.none.fl_str_mv TDX (Tesis Doctorals en Xarxa)
reponame:TDR. Tesis Doctorales en Red
instname:CBUC, CESCA
instname_str CBUC, CESCA
reponame_str TDR. Tesis Doctorales en Red
collection TDR. Tesis Doctorales en Red
repository.name.fl_str_mv
repository.mail.fl_str_mv
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spelling Rhodium-catalyzed cyclization reactions of 1,5-bisallenes involving alkenes and alkynes: experimental and theoretical studiesVila Vadrí, JordiCatàlisiCatálisisCatalysisRodiRodioRhodiumReaccions de ciclacióReacciones de ciclaciónCyclization reactionsAl·lensAlenosAllenesCàlculs DFTCálculos DFTDFT calculationsCicloaddicióCicloadiciónCycloaddition547The development of novel catalytic methodologies involving the formation of carbon – carbon/heteroatom bonds to produce cyclic systems constitutes a field of great interest in the modern synthetic organic chemistry. Over the last 30 years, the combined use of transition metals with allenes allowed considerable progress in this field. Allenes are cumulated dienes, constituted by two perpendicular double bonds. The unsaturation spread over three contiguous carbons gives allenes additional versatility in cyclization reactions compared to other unsaturations, such as alkenes or alkynes, although the control of the selectivity becomes more challenging when allenes are used. One paradigmatic process to produce cyclic systems is the transition metal-catalyzed [2+2+2] cycloaddition reaction, which enable the simultaneous formation of several bonds and/or stereogenic centers in a single step to produce six-membered rings in perfect atom economy. Our group has developed several rhodium-catalyzed [2+2+2] cycloaddition reactions and has made great mechanistic contributions employing DFT calculations and experimental techniques. Regarding the use of allenes, our group studied the rhodium(I)-catalyzed intramolecular [2+2+2] cycloaddition of linear substrates accommodating allenes and alkynes and/or alkenes. However, [2+2+2] cycloadditions involving two allenes with another unsaturated carbon – carbon bond remain scarce. Considering this, and as part of our continuous interest in the use of allenes, we envisaged the development of partially intramolecular [2+2+2] cycloaddition reactions of 1,5-bisallenes with alkenes and alkynes. Although 1,5-bisallenes exhibited rich chemistry with transition metals, very few examples were reported involving the incorporation of a third unsaturated partner in a cycloaddition reaction. The main goal set within the context of this thesis was to develop new rhodium(I)-catalyzed cycloaddition reactions of 1,5-bisallenes with alkenes and alkynes. As reported in chapter 3, we have succeeded in reacting 1,5-bisallenes with a series of alkenes employing rhodium(I) catalysis. The reaction provided a series of polycyclic dihydroazepine and dihydrooxepine derivatives in a single step and perfect atom economy. The results obtained in chapter 3 allowed us to develop an homodimerization process of 1,5-bisallenes to obtain spirocyclic derivatives featuring six- and seven- membered rings in the spiro carbon (chapter 4). The process was found to be highly chemo- and regioselective, affording a single isomer out of six possible adducts. Moving forward to the use of alkynes, in chapter 5 and 6 we accomplished the proposed objectives by reacting 1,5-bisallenes and alkynes to form cis-3,4-arylvinyl pyrrolidines and cyclopentanes (chapter 5), and bicyclic trans-fused 3,6-dimethylenecyclohex-1-ene derivatives (chapter 6) from 1,5-bisallenes and alkynes using rhodium(I) as a catalyst. Additionally, the mechanism of the reaction was studied in all the developed protocols by means of DFT calculations and experimental techniques that allowed justify the selectivities observedEl desenvolupament de noves metodologies catalítiques per generar sistemes cíclics involucrant la formació d’enllaços carboni – carboni/heteroàtom és de gran interès en l’àmbit de la química orgànica sintètica moderna. L’ús combinat d’al·lens i metalls de transició ha permès considerables progressos en aquest àmbit durant els últims 30 anys. Els al·lens son diens acumulats, formats per dos dobles enllaços perpendiculars. Al tenir dues insaturacions repartides en tres carbonis, els al·lens presenten una versatilitat addicional en reaccions de ciclació quan els comparem amb altres insaturacions, com els alquens o els alquins. No obstant, el control de la selectivitat resulta més complicat quan utilitzem al·lens. Un procés exemplar per generar sistemes cíclics és la cicloaddició [2+2+2] catalitzada per metalls de transició, que permet la formació simultània de varis enllaços i/o centres estereogènics en una sola etapa per produir anells de sis baules amb economia atòmica perfecta. El nostre grup ha desenvolupat diverses cicloaddicions [2+2+2] catalitzades per rodi i ha fet importants contribucions a l’estudi del mecanisme de la reacció emparant càlculs DFT i tècniques experimentals. Pel que fa a l’ús d’al·lens, el grup ha estudiat la cicloaddició [2+2+2] intramolecular de substrats lineals incorporant al·lens i alquens i/o alquins. No obstant, els exemples de reaccions de cicloaddició [2+2+2] involucrant dos al·lens amb una tercera insaturació son escassos. Considerant aquest fet, i el nostre interès en l’ús d’al·lens, vam concebre el desenvolupament de reaccions de cicloaddició [2+2+2] parcialment intramoleculars entre 1,5-bisal·lens incorporant alquens o alquins. Tot i que els 1,5-bisal·lens han demostrat tenir una química rica quan es combinen amb metalls de transició, son molt pocs els exemples de cicloaddicions on s’hi incorpori una tercera insaturació. El principal objectiu d’aquesta tesi va ser desenvolupar noves cicloaddicions catalitzades per rodi d’1,5-bisal·lens amb alquens i alquins. Al capítol 3, es va fer reaccionar satisfactòriament els 1,5-bisal·lens amb diversos alquens emparant rodi(I) com a catalitzador. La reacció forní derivats policíclics de dihidroazepina i dihidrooxapina en una sola etapa i economia atòmica perfecta. Els resultats obtinguts d’aquest capítol, ens van permetre desenvolupar un procés d’homodimerització de diferents 1,5-bisal·lens per generar compostos espirocíclics, exhibint anells de sis i set baules al carboni espirànic (capítol 4). El procés va resultar ser completament quimio- i regioselectiu, obtenint només un isòmer dels sis possibles. Avançant cap a l’ús d’alquins, als capítols 5 i 6 vam aconseguir els objectius marcats fent reaccionar els 1,5-bisal·lens amb alquins per formar, en un cas, cis-3,4-arilvinil pirrolidines i ciclopentans (capítol 5), i en l’altre, derivats bicicle en fusió trans de 3,6-dimetilenciclohex-1-ens (capítol 6). Altrament, els mecanismes de les reaccions van ser estudiats en tots els processos utilitzant càlculs computacionals DFT i tècniques experimentals que en van permetre explicar les diferents selectivitats observadesPrograma de Doctorat en QuímicaUniversitat de GironaRoglans i Ribas, AnnaPla i Quintana, AnnaUniversitat de Girona. Departament de QuímicaUniversitat de Girona. Institut de Química Computacional i Catàlisi202320232023info:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/publishedVersion237 p.application/pdfhttp://hdl.handle.net/10803/688847TDX (Tesis Doctorals en Xarxa)reponame:TDR. Tesis Doctorales en Redinstname:CBUC, CESCAInglésL'accés als continguts d'aquesta tesi queda condicionat a l'acceptació de les condicions d'ús establertes per la següent llicència Creative Commons: http://creativecommons.org/licenses/by-nc/4.0/http://creativecommons.org/licenses/by-nc/4.0/info:eu-repo/semantics/openAccessoai:www.tdx.cat:10803/6888472026-06-14T12:46:07Z
score 15,300724

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