English   español  
Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/154841
Share/Impact:
Statistics
logo share SHARE logo core CORE   Add this article to your Mendeley library MendeleyBASE

Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL | DATACITE
Exportar a otros formatos:

Title

Computational mechanistic study of thionation of carbonyl compounds with Lawesson's reagent

AuthorsLegnani, Laura; Toma, L.; Caramella, Pierluigi; Chiacchio, Maria A.; Giofrè, S.; Delso, J. Ignacio; Tejero, Tomás ; Merino, Pedro
Issue Date2016
PublisherAmerican Chemical Society
CitationJournal of Organic Chemistry 81(17): 7733-7740 (2016)
AbstractThe thionation reaction of carbonyl compounds with Lawesson's reagent (LR) has been studied using density functional theory methods and topological analyses. After dissociation of LR, the reaction takes place through a two-step mechanism involving (i) a concerted cycloaddition between one monomer and the carbonyl compound to form a four-membered intermediate and (ii) a cycloreversion leading to the thiocarbonyl derivative and phenyl(thioxo)phosphine oxide. Topological analyses confirmed the concertedness and asynchronicity of the process. The second step is the rate-limiting one, and the whole process resembles the currently accepted mechanism for the lithium salt-free Wittig reaction. No zwitterionic intermediates are formed during the reaction, although stabilizing electrostatic interactions are present in initial stages. Phenyl(thioxo)phosphine oxide formed in the thionation reaction is capable of performing a second thionation, although with energy barriers higher than the first one. The driving force of the thionation reactions is the formation of trimers from the resulting monomers. In agreement with experimental observations, the amides are the most reactive when compared with esters, aldehydes, and ketones and the reaction is slightly influenced by the polarity of the solvent. Whereas for amides and esters substituents have little effect, aldehydes and ketones are influenced by both steric and electronic effects.
Publisher version (URL)https://doi.org/10.1021/acs.joc.6b01420
URIhttp://hdl.handle.net/10261/154841
DOIhttp://dx.doi.org/10.1021/acs.joc.6b01420
Identifiersdoi: 10.1021/acs.joc.6b01420
e-issn: 1520-6904
issn: 0022-3263
Appears in Collections:(ISQCH) Artículos
Files in This Item:
File Description SizeFormat 
Lawesson.pdf1,86 MBAdobe PDFThumbnail
View/Open
Show full item record
Review this work
 


WARNING: Items in Digital.CSIC are protected by copyright, with all rights reserved, unless otherwise indicated.