NDLI: Reactions of heterocumulenes with organometallic reagents: XVIII. Quantum-chemical study on the mechanisms of formation of thiophene ring from lithium and potassium buta-2,3-dienimidothioates

Content Provider	Springer Nature Link
Author	Shagun, V. A. Nedolya, N. A.
Copyright Year	2011
Abstract	Thermodynamic stabilities of different isomers and tautomers of lithium and potassium buta-2,3-dienimidothioates (ambident N,S-centered anionic adducts derived from methoxyallenyl carbanion and methyl isothiocyanate) as real or potential precursors of 3-methoxy-N,N-dimethylthiophen-2-amine were estimated by quantum-chemical calculations in terms of the density functional theory. Gradient channels corresponding to concerted (one-step) and stepwise (two-step) mechanisms of formation of thiophene ring from the most stable conformers and tautomers were localized. The formation of thiophene structure from lithium and potassium buta-2,3-dienimidothioates in two steps via intramolecular cyclization to thiophen-2(5H)-ylidene anion and its isomerization into thienylamide was found to be more probable. The activation barriers in both stepwise and concerted cyclization mechanisms considerably decrease in going from lithium to potassium as counterion.
Starting Page	1841
Ending Page	1850
Page Count	10
File Format	PDF
ISSN	10704280
Journal	Russian Journal of Organic Chemistry
Volume Number	47
Issue Number	12
e-ISSN	16083393
Language	English
Publisher	SP MAIK Nauka/Interperiodica
Publisher Date	2012-01-05
Publisher Place	Dordrecht
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Organic Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry

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Reactions of heterocumulenes with organometallic reagents: XVIII. Quantum-chemical study on the mechanisms of formation of thiophene ring from lithium and potassium buta-2,3-dienimidothioates