The 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.

Legnani, L., Toma, L., Caramella, P., Chiacchio, M., Giofrè, S., Delso, I., et al. (2016). Computational Mechanistic Study of Thionation of Carbonyl Compounds with Lawesson's Reagent. JOURNAL OF ORGANIC CHEMISTRY, 81(17), 7733-7740 [10.1021/acs.joc.6b01420].

Computational Mechanistic Study of Thionation of Carbonyl Compounds with Lawesson's Reagent

LEGNANI, LAURA
;
2016

Abstract

The 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.
Articolo in rivista - Articolo scientifico
Organic Chemistry
English
7733
7740
8
Legnani, L., Toma, L., Caramella, P., Chiacchio, M., Giofrè, S., Delso, I., et al. (2016). Computational Mechanistic Study of Thionation of Carbonyl Compounds with Lawesson's Reagent. JOURNAL OF ORGANIC CHEMISTRY, 81(17), 7733-7740 [10.1021/acs.joc.6b01420].
Legnani, L; Toma, L; Caramella, P; Chiacchio, M; Giofrè, S; Delso, I; Tejero, T; Merino, P
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/351984
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