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10.1021/acs.joc.9b01014
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Título: | Chemodivergent Conversion of Ketenimines Bearing Cyclic Dithioacetalic Units into Isoquinoline-1-thiones or Quinolin-4-ones as a Function of the Acetalic Ring Size |
Fecha de publicación: | 21-jun-2019 |
Fecha de defensa / creación: | 2019 |
Cita bibliográfica: | J. Org. Chem. 2019, 84, 8140–8150. |
ISSN: | 0022-3263 1520-6904 |
Materias relacionadas: | CDU::5 - Ciencias puras y naturales::54 - Química::547 - Química orgánica |
Palabras clave: | HYDROGEN-ATOM TRANSFER THERMAL CYCLIZATION TANDEM PROCESSES DFT CALCULATIONS HETEROCYCLES |
Resumen: | C-Alkoxycarbonyl-C-phenyl-N-aryl ketenimines bearing 1,3-dithiolan-2-yl or 1,3-dithian-2-yl substituents at ortho position of the C-phenyl ring, respectively, transform into isoquino-line-1-thiones and quinolin-4-ones under thermal treatment in toluene solution. The formation of isoquinolinethiones involves a rare degradation of the 1,3-dithiolane ring, whereas, in contrast, the 1,3-dithiane ring remains intact during the reaction course leading to quinolin-4-ones. Computational density functional theory results support that the kinetically favorable mechanism for the formation of isoquinoline-l-thiones proceeds through a [1,5]-hydride shift/6 pi-electrocyclization cascade, followed by a thiirane extrusion process. Alternative mechanistic paths showing interesting electronic reorganization processes have been also scrutinized but resulted not competitive on energetic grounds. |
Autor/es principal/es: | Alajarín, Mateo Marin-Luna, Marta Sanchez-Andrada, Pilar Vidal, Angel |
Facultad/Departamentos/Servicios: | Facultades, Departamentos, Servicios y Escuelas::Departamentos de la UMU::Química Orgánica |
Versión del editor: | https://pubs.acs.org/doi/full/10.1021/acs.joc.9b01014 |
URI: | http://hdl.handle.net/10201/102641 |
DOI: | 10.1021/acs.joc.9b01014 |
Tipo de documento: | info:eu-repo/semantics/article |
Número páginas / Extensión: | 18 |
Derechos: | info:eu-repo/semantics/openAccess Atribución-NoComercial-SinDerivadas 3.0 España |
Aparece en las colecciones: | Artículos: Química Orgánica |
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19JOC_AV_Chemodivergent Conversion of Ketenimines Bearing Cyclic Dithioacetalic.pdf | 560,75 kB | Adobe PDF | Visualizar/Abrir |
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