Green synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran and its subsequent enantioselective epoxidation

Autores
Romanelli, Gustavo Pablo; Sathicq, Angel Gabriel; Vazquez, Patricia Graciela; Villa, Aida; Alarcón, Edwin; Grajales, Edwing; Cubillos, Jairo
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The clean synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran epoxide starting from 3-methyl-2-butenal is reported using recyclable catalysts. H4PMo11VO40 (PMo11V) and (PyH)3HPMo11VO40(Py3–PMo11V) Keggin-type heteropolyacids were used to synthesize 6-cyano-2,2-dimethyl-2-H-1-benzopyran in two steps with 35% yield. This is an alternative procedure to the traditional methodology with pyridine or picoline as catalyst, where 6-cyano-2,2-dimethyl-2-H-1-benzopyran is obtained by condensation of 4-cyanophenol with 1,1-diethoxy-3-methyl-2-butene. The 6-cyano-2,2-dimethyl-2-H-1-benzopyran epoxide was obtained using Jacobsen-type catalysts, and in situ generated dimethyldioxirane (DMD) as oxidizing agent, that in comparison to m-CPBA/4-NMO and NaOCl/4-PPNO did not degrade the catalyst. In presence of 4-phenylpyridine N-oxide (4-PPNO) at 4 ◦C, enantioselectivities of 87% for 3S,4S-epoxide and 68% for 3R,4R-epoxide were obtained with the S,S- and R,R-Jacobsen catalysts,respectively. Overall yield was approximately 17% for 3S,4S-epoxide
Fil: Romanelli, Gustavo Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina
Fil: Sathicq, Angel Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina
Fil: Vazquez, Patricia Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina
Fil: Villa, Aida. Universidad de Antioquia. Environmental Catalysis Research Group Chemical Engineering Department; Colombia
Fil: Alarcón, Edwin. Universidad de Antioquia. Environmental Catalysis Research Group Chemical Engineering Department; Colombia
Fil: Grajales, Edwing. Universidad de Antioquia. Environmental Catalysis Research Group Chemical Engineering Department; Colombia
Fil: Cubillos, Jairo. Universidad Pedagógica y Tecnológica de Colombia. Facultad de Ciencias. Escuela de Ciencias Químicas, ; Colombia
Materia
Heteropolyacids
Jacobsen-Type Catalyst
6-Cyano-2,2-Dimethyl-2-H-1-Benzopyran
Chromene Epoxide
Sustainable Synthesis
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/8403
Acceder
id CONICETDig_7b45c5162d1ddf8c78d5ad1c4ee474b4
oai_identifier_str oai:ri.conicet.gov.ar:11336/8403
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Green synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran and its subsequent enantioselective epoxidationRomanelli, Gustavo PabloSathicq, Angel GabrielVazquez, Patricia GracielaVilla, AidaAlarcón, EdwinGrajales, EdwingCubillos, JairoHeteropolyacidsJacobsen-Type Catalyst6-Cyano-2,2-Dimethyl-2-H-1-BenzopyranChromene EpoxideSustainable Synthesishttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2The clean synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran epoxide starting from 3-methyl-2-butenal is reported using recyclable catalysts. H4PMo11VO40 (PMo11V) and (PyH)3HPMo11VO40(Py3–PMo11V) Keggin-type heteropolyacids were used to synthesize 6-cyano-2,2-dimethyl-2-H-1-benzopyran in two steps with 35% yield. This is an alternative procedure to the traditional methodology with pyridine or picoline as catalyst, where 6-cyano-2,2-dimethyl-2-H-1-benzopyran is obtained by condensation of 4-cyanophenol with 1,1-diethoxy-3-methyl-2-butene. The 6-cyano-2,2-dimethyl-2-H-1-benzopyran epoxide was obtained using Jacobsen-type catalysts, and in situ generated dimethyldioxirane (DMD) as oxidizing agent, that in comparison to m-CPBA/4-NMO and NaOCl/4-PPNO did not degrade the catalyst. In presence of 4-phenylpyridine N-oxide (4-PPNO) at 4 ◦C, enantioselectivities of 87% for 3S,4S-epoxide and 68% for 3R,4R-epoxide were obtained with the S,S- and R,R-Jacobsen catalysts,respectively. Overall yield was approximately 17% for 3S,4S-epoxideFil: Romanelli, Gustavo Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas; ArgentinaFil: Sathicq, Angel Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas; ArgentinaFil: Vazquez, Patricia Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas; ArgentinaFil: Villa, Aida. Universidad de Antioquia. Environmental Catalysis Research Group Chemical Engineering Department; ColombiaFil: Alarcón, Edwin. Universidad de Antioquia. Environmental Catalysis Research Group Chemical Engineering Department; ColombiaFil: Grajales, Edwing. Universidad de Antioquia. Environmental Catalysis Research Group Chemical Engineering Department; ColombiaFil: Cubillos, Jairo. Universidad Pedagógica y Tecnológica de Colombia. Facultad de Ciencias. Escuela de Ciencias Químicas, ; ColombiaElsevier Science2014-11-29info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/8403Romanelli, Gustavo Pablo; Sathicq, Angel Gabriel; Vazquez, Patricia Graciela; Villa, Aida; Alarcón, Edwin; et al.; Green synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran and its subsequent enantioselective epoxidation; Elsevier Science; Journal Of Molecular Catalysis A: Chemical; 398; 29-11-2014; 11-161381-1169enginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.molcata.2014.11.027info:eu-repo/semantics/altIdentifier/url/http://ac.els-cdn.com/S1381116914005378/1-s2.0-S1381116914005378-main.pdf?_tid=60a978f4-b31f-11e6-9c99-00000aab0f26&acdnat=1480085983_f3ea60085d36745985a67908a1547ee7info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:41:59Zoai:ri.conicet.gov.ar:11336/8403instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-15 14:42:00.078CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Green synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran and its subsequent enantioselective epoxidation
title Green synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran and its subsequent enantioselective epoxidation
spellingShingle Green synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran and its subsequent enantioselective epoxidation
Romanelli, Gustavo Pablo
Heteropolyacids
Jacobsen-Type Catalyst
6-Cyano-2,2-Dimethyl-2-H-1-Benzopyran
Chromene Epoxide
Sustainable Synthesis
title_short Green synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran and its subsequent enantioselective epoxidation
title_full Green synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran and its subsequent enantioselective epoxidation
title_fullStr Green synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran and its subsequent enantioselective epoxidation
title_full_unstemmed Green synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran and its subsequent enantioselective epoxidation
title_sort Green synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran and its subsequent enantioselective epoxidation
dc.creator.none.fl_str_mv Romanelli, Gustavo Pablo
Sathicq, Angel Gabriel
Vazquez, Patricia Graciela
Villa, Aida
Alarcón, Edwin
Grajales, Edwing
Cubillos, Jairo
author Romanelli, Gustavo Pablo
author_facet Romanelli, Gustavo Pablo
Sathicq, Angel Gabriel
Vazquez, Patricia Graciela
Villa, Aida
Alarcón, Edwin
Grajales, Edwing
Cubillos, Jairo
author_role author
author2 Sathicq, Angel Gabriel
Vazquez, Patricia Graciela
Villa, Aida
Alarcón, Edwin
Grajales, Edwing
Cubillos, Jairo
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Heteropolyacids
Jacobsen-Type Catalyst
6-Cyano-2,2-Dimethyl-2-H-1-Benzopyran
Chromene Epoxide
Sustainable Synthesis
topic Heteropolyacids
Jacobsen-Type Catalyst
6-Cyano-2,2-Dimethyl-2-H-1-Benzopyran
Chromene Epoxide
Sustainable Synthesis
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv The clean synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran epoxide starting from 3-methyl-2-butenal is reported using recyclable catalysts. H4PMo11VO40 (PMo11V) and (PyH)3HPMo11VO40(Py3–PMo11V) Keggin-type heteropolyacids were used to synthesize 6-cyano-2,2-dimethyl-2-H-1-benzopyran in two steps with 35% yield. This is an alternative procedure to the traditional methodology with pyridine or picoline as catalyst, where 6-cyano-2,2-dimethyl-2-H-1-benzopyran is obtained by condensation of 4-cyanophenol with 1,1-diethoxy-3-methyl-2-butene. The 6-cyano-2,2-dimethyl-2-H-1-benzopyran epoxide was obtained using Jacobsen-type catalysts, and in situ generated dimethyldioxirane (DMD) as oxidizing agent, that in comparison to m-CPBA/4-NMO and NaOCl/4-PPNO did not degrade the catalyst. In presence of 4-phenylpyridine N-oxide (4-PPNO) at 4 ◦C, enantioselectivities of 87% for 3S,4S-epoxide and 68% for 3R,4R-epoxide were obtained with the S,S- and R,R-Jacobsen catalysts,respectively. Overall yield was approximately 17% for 3S,4S-epoxide
Fil: Romanelli, Gustavo Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina
Fil: Sathicq, Angel Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina
Fil: Vazquez, Patricia Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina
Fil: Villa, Aida. Universidad de Antioquia. Environmental Catalysis Research Group Chemical Engineering Department; Colombia
Fil: Alarcón, Edwin. Universidad de Antioquia. Environmental Catalysis Research Group Chemical Engineering Department; Colombia
Fil: Grajales, Edwing. Universidad de Antioquia. Environmental Catalysis Research Group Chemical Engineering Department; Colombia
Fil: Cubillos, Jairo. Universidad Pedagógica y Tecnológica de Colombia. Facultad de Ciencias. Escuela de Ciencias Químicas, ; Colombia
description The clean synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran epoxide starting from 3-methyl-2-butenal is reported using recyclable catalysts. H4PMo11VO40 (PMo11V) and (PyH)3HPMo11VO40(Py3–PMo11V) Keggin-type heteropolyacids were used to synthesize 6-cyano-2,2-dimethyl-2-H-1-benzopyran in two steps with 35% yield. This is an alternative procedure to the traditional methodology with pyridine or picoline as catalyst, where 6-cyano-2,2-dimethyl-2-H-1-benzopyran is obtained by condensation of 4-cyanophenol with 1,1-diethoxy-3-methyl-2-butene. The 6-cyano-2,2-dimethyl-2-H-1-benzopyran epoxide was obtained using Jacobsen-type catalysts, and in situ generated dimethyldioxirane (DMD) as oxidizing agent, that in comparison to m-CPBA/4-NMO and NaOCl/4-PPNO did not degrade the catalyst. In presence of 4-phenylpyridine N-oxide (4-PPNO) at 4 ◦C, enantioselectivities of 87% for 3S,4S-epoxide and 68% for 3R,4R-epoxide were obtained with the S,S- and R,R-Jacobsen catalysts,respectively. Overall yield was approximately 17% for 3S,4S-epoxide
publishDate 2014
dc.date.none.fl_str_mv 2014-11-29
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/8403
Romanelli, Gustavo Pablo; Sathicq, Angel Gabriel; Vazquez, Patricia Graciela; Villa, Aida; Alarcón, Edwin; et al.; Green synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran and its subsequent enantioselective epoxidation; Elsevier Science; Journal Of Molecular Catalysis A: Chemical; 398; 29-11-2014; 11-16
1381-1169
url http://hdl.handle.net/11336/8403
identifier_str_mv Romanelli, Gustavo Pablo; Sathicq, Angel Gabriel; Vazquez, Patricia Graciela; Villa, Aida; Alarcón, Edwin; et al.; Green synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran and its subsequent enantioselective epoxidation; Elsevier Science; Journal Of Molecular Catalysis A: Chemical; 398; 29-11-2014; 11-16
1381-1169
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molcata.2014.11.027
info:eu-repo/semantics/altIdentifier/url/http://ac.els-cdn.com/S1381116914005378/1-s2.0-S1381116914005378-main.pdf?_tid=60a978f4-b31f-11e6-9c99-00000aab0f26&acdnat=1480085983_f3ea60085d36745985a67908a1547ee7
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.22299

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