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Chemodivergent Conversion of Ketenimines Bearing Cyclic Dithioacetalic Units into Isoquinoline-1-thiones or Quinolin-4-ones as a Function of the Acetalic Ring Size

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19JOC_AV_Chemodivergent Conversion of Ketenimines Bearing Cyclic Dithioacetalic.pdf(560.75 KB)
Date
2019-06-21
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Authors
Alajarín, Mateo ; Marin-Luna, Marta ; Sanchez-Andrada, Pilar ; Vidal, Angel
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Publisher
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Química Orgánica
DOI
10.1021/acs.joc.9b01014
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info:eu-repo/semantics/article
Description
Abstract
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.
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HYDROGEN-ATOM TRANSFER , THERMAL CYCLIZATION , TANDEM PROCESSES , DFT CALCULATIONS , HETEROCYCLES
Citation
J. Org. Chem. 2019, 84, 8140–8150.
URI
http://hdl.handle.net/10201/102641
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