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

Autores
Romanelli, Gustavo Pablo; Sathicq, Ángel Gabriel; Vázquez, Patricia Graciela; Villa, Aída Luz; Alarcón, Edwin; Grajales, Edwing; Cubillos, Jairo
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Abstract 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.
Facultad de Ciencias Exactas
Centro de Investigación y Desarrollo en Ciencias Aplicadas
Materia
Ciencias Exactas
Química
Heteropolyacids
Jacobsen-type catalyst
Sustainable synthesis
6-Cyano-2,2-dimethyl-2-H-1-benzopyran
Chromene epoxide
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/128792
Acceder
id SEDICI_f5d3428ee95ede4db55b8fca1792eb0e
oai_identifier_str oai:sedici.unlp.edu.ar:10915/128792
network_acronym_str SEDICI
repository_id_str 1329
network_name_str SEDICI (UNLP)
spelling Green synthesis of 6-cyano-2,2-dimethyl-2-H-1-benzopyran and its subsequent enantioselective epoxidationRomanelli, Gustavo PabloSathicq, Ángel GabrielVázquez, Patricia GracielaVilla, Aída LuzAlarcón, EdwinGrajales, EdwingCubillos, JairoCiencias ExactasQuímicaHeteropolyacidsJacobsen-type catalystSustainable synthesis6-Cyano-2,2-dimethyl-2-H-1-benzopyranChromene epoxideAbstract 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.Facultad de Ciencias ExactasCentro de Investigación y Desarrollo en Ciencias Aplicadas2015-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf11-16http://sedici.unlp.edu.ar/handle/10915/128792enginfo:eu-repo/semantics/altIdentifier/issn/1381-1169info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molcata.2014.11.027info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-10-15T11:22:49Zoai:sedici.unlp.edu.ar:10915/128792Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-10-15 11:22:49.344SEDICI (UNLP) - Universidad Nacional de La Platafalse
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
Ciencias Exactas
Química
Heteropolyacids
Jacobsen-type catalyst
Sustainable synthesis
6-Cyano-2,2-dimethyl-2-H-1-benzopyran
Chromene epoxide
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, Ángel Gabriel
Vázquez, Patricia Graciela
Villa, Aída Luz
Alarcón, Edwin
Grajales, Edwing
Cubillos, Jairo
author Romanelli, Gustavo Pablo
author_facet Romanelli, Gustavo Pablo
Sathicq, Ángel Gabriel
Vázquez, Patricia Graciela
Villa, Aída Luz
Alarcón, Edwin
Grajales, Edwing
Cubillos, Jairo
author_role author
author2 Sathicq, Ángel Gabriel
Vázquez, Patricia Graciela
Villa, Aída Luz
Alarcón, Edwin
Grajales, Edwing
Cubillos, Jairo
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Ciencias Exactas
Química
Heteropolyacids
Jacobsen-type catalyst
Sustainable synthesis
6-Cyano-2,2-dimethyl-2-H-1-benzopyran
Chromene epoxide
topic Ciencias Exactas
Química
Heteropolyacids
Jacobsen-type catalyst
Sustainable synthesis
6-Cyano-2,2-dimethyl-2-H-1-benzopyran
Chromene epoxide
dc.description.none.fl_txt_mv Abstract 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.
Facultad de Ciencias Exactas
Centro de Investigación y Desarrollo en Ciencias Aplicadas
description Abstract 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 2015
dc.date.none.fl_str_mv 2015-03
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
Articulo
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://sedici.unlp.edu.ar/handle/10915/128792
url http://sedici.unlp.edu.ar/handle/10915/128792
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/issn/1381-1169
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molcata.2014.11.027
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
dc.format.none.fl_str_mv application/pdf
11-16
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instname:Universidad Nacional de La Plata
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reponame_str SEDICI (UNLP)
collection SEDICI (UNLP)
instname_str Universidad Nacional de La Plata
instacron_str UNLP
institution UNLP
repository.name.fl_str_mv SEDICI (UNLP) - Universidad Nacional de La Plata
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