Efficient isomerization of α-pinene oxide to campholenic aldehyde promoted by a mixed-ring analogue of molybdenocene

Detalhes bibliográficos
Autor(a) principal: Bruno, Sofia M.
Data de Publicação: 2019
Outros Autores: Valente, Anabela A., Pillinger, Martyn, Amelse, Jeffrey, Romão, Carlos C., Gonçalves, Isabel S.
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
Texto Completo: http://hdl.handle.net/10773/26614
Resumo: The MoIV complex [(eta5-indenyl)(eta5-cyclopentadienyl)Mo(MeCN)2](BF4)2 (1) has been used to promote two acid-catalyzed epoxide ring-opening reactions under ambient conditions. The alcoholysis of styrene oxide in neat ethanol gave 2-ethoxy-2-phenylethanol in quantitative yield within 10 min. The use of an ionic liquid (IL) as cosolvent benefitted catalyst solubility and recycling while not impairing catalytic performance. Complex 1 in 1,2-dichloroethane was effective for the isomerization of alpha-pinene oxide to campholenic aldehyde (CPA), leading to 87% yield at 1 h reaction. The same yield could be achieved within 1 min by using the IL [Choline][NTf2] as solvent. CPA yields at 1 min reached near-quantitative values (98%) upon recycling of the catalyst/IL mixture, demonstrating an unparalleled combination of activity, selectivity and recyclability for this commercially important reaction. Considering the catalytic features of the 1/IL system, a CPA process flow diagram is proposed and compared to patented technology.
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spelling Efficient isomerization of α-pinene oxide to campholenic aldehyde promoted by a mixed-ring analogue of molybdenoceneRenewable resourcesTerpenesRearrangementHomogeneous catalysisMolybdenumMetallocenesLewis acidsIonic liquidsThe MoIV complex [(eta5-indenyl)(eta5-cyclopentadienyl)Mo(MeCN)2](BF4)2 (1) has been used to promote two acid-catalyzed epoxide ring-opening reactions under ambient conditions. The alcoholysis of styrene oxide in neat ethanol gave 2-ethoxy-2-phenylethanol in quantitative yield within 10 min. The use of an ionic liquid (IL) as cosolvent benefitted catalyst solubility and recycling while not impairing catalytic performance. Complex 1 in 1,2-dichloroethane was effective for the isomerization of alpha-pinene oxide to campholenic aldehyde (CPA), leading to 87% yield at 1 h reaction. The same yield could be achieved within 1 min by using the IL [Choline][NTf2] as solvent. CPA yields at 1 min reached near-quantitative values (98%) upon recycling of the catalyst/IL mixture, demonstrating an unparalleled combination of activity, selectivity and recyclability for this commercially important reaction. Considering the catalytic features of the 1/IL system, a CPA process flow diagram is proposed and compared to patented technology.American Chemical Society2020-08-19T00:00:00Z2019-08-19T00:00:00Z2019-08-19info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10773/26614eng2168-048510.1021/acssuschemeng.9b03087Bruno, Sofia M.Valente, Anabela A.Pillinger, MartynAmelse, JeffreyRomão, Carlos C.Gonçalves, Isabel S.info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2024-05-06T04:21:39Zoai:ria.ua.pt:10773/26614Portal AgregadorONGhttps://www.rcaap.pt/oai/openairemluisa.alvim@gmail.comopendoar:71602024-05-06T04:21:39Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse
dc.title.none.fl_str_mv Efficient isomerization of α-pinene oxide to campholenic aldehyde promoted by a mixed-ring analogue of molybdenocene
title Efficient isomerization of α-pinene oxide to campholenic aldehyde promoted by a mixed-ring analogue of molybdenocene
spellingShingle Efficient isomerization of α-pinene oxide to campholenic aldehyde promoted by a mixed-ring analogue of molybdenocene
Bruno, Sofia M.
Renewable resources
Terpenes
Rearrangement
Homogeneous catalysis
Molybdenum
Metallocenes
Lewis acids
Ionic liquids
title_short Efficient isomerization of α-pinene oxide to campholenic aldehyde promoted by a mixed-ring analogue of molybdenocene
title_full Efficient isomerization of α-pinene oxide to campholenic aldehyde promoted by a mixed-ring analogue of molybdenocene
title_fullStr Efficient isomerization of α-pinene oxide to campholenic aldehyde promoted by a mixed-ring analogue of molybdenocene
title_full_unstemmed Efficient isomerization of α-pinene oxide to campholenic aldehyde promoted by a mixed-ring analogue of molybdenocene
title_sort Efficient isomerization of α-pinene oxide to campholenic aldehyde promoted by a mixed-ring analogue of molybdenocene
author Bruno, Sofia M.
author_facet Bruno, Sofia M.
Valente, Anabela A.
Pillinger, Martyn
Amelse, Jeffrey
Romão, Carlos C.
Gonçalves, Isabel S.
author_role author
author2 Valente, Anabela A.
Pillinger, Martyn
Amelse, Jeffrey
Romão, Carlos C.
Gonçalves, Isabel S.
author2_role author
author
author
author
author
dc.contributor.author.fl_str_mv Bruno, Sofia M.
Valente, Anabela A.
Pillinger, Martyn
Amelse, Jeffrey
Romão, Carlos C.
Gonçalves, Isabel S.
dc.subject.por.fl_str_mv Renewable resources
Terpenes
Rearrangement
Homogeneous catalysis
Molybdenum
Metallocenes
Lewis acids
Ionic liquids
topic Renewable resources
Terpenes
Rearrangement
Homogeneous catalysis
Molybdenum
Metallocenes
Lewis acids
Ionic liquids
description The MoIV complex [(eta5-indenyl)(eta5-cyclopentadienyl)Mo(MeCN)2](BF4)2 (1) has been used to promote two acid-catalyzed epoxide ring-opening reactions under ambient conditions. The alcoholysis of styrene oxide in neat ethanol gave 2-ethoxy-2-phenylethanol in quantitative yield within 10 min. The use of an ionic liquid (IL) as cosolvent benefitted catalyst solubility and recycling while not impairing catalytic performance. Complex 1 in 1,2-dichloroethane was effective for the isomerization of alpha-pinene oxide to campholenic aldehyde (CPA), leading to 87% yield at 1 h reaction. The same yield could be achieved within 1 min by using the IL [Choline][NTf2] as solvent. CPA yields at 1 min reached near-quantitative values (98%) upon recycling of the catalyst/IL mixture, demonstrating an unparalleled combination of activity, selectivity and recyclability for this commercially important reaction. Considering the catalytic features of the 1/IL system, a CPA process flow diagram is proposed and compared to patented technology.
publishDate 2019
dc.date.none.fl_str_mv 2019-08-19T00:00:00Z
2019-08-19
2020-08-19T00:00:00Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
format article
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://hdl.handle.net/10773/26614
url http://hdl.handle.net/10773/26614
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv 2168-0485
10.1021/acssuschemeng.9b03087
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação
instacron:RCAAP
instname_str Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação
instacron_str RCAAP
institution RCAAP
reponame_str Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
collection Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
repository.name.fl_str_mv Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação
repository.mail.fl_str_mv mluisa.alvim@gmail.com
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