Please use this identifier to cite or link to this item: https://scidar.kg.ac.rs/handle/123456789/12333
Title: DFT study of the mechanism of the phenylselenoetherification reaction of linalool
Authors: Janković, Nenad
Markovic, Svetlana
Bugarčić Z.
Issue Date: 2014
Abstract: A systematic study of the mechanism of phenylselenoetherification of a naturally occurring alcohol linalool with PhSe+ was performed at the B3LYP/6-311+G(d,p) level of theory, in conjunction with the CPCM solvation model. The syn and anti reaction pathways were examined in the absence and presence of some Lewis bases (quinoline, piperidine, pyridine, and triethylamine) as catalysts. It was found that the reaction occurs via the phenylseleniranium intermediate, which further suffers a nucleophilic attack of the oxygen to two olefinic carbon atoms. This intramolecular cyclization yields 5-ethenyl-5-methyl-2-[2-(phenylseleno)-prop-2-yl]tetrahydrofuran as the major product and 6-ethenyl-2,2,6-trimethyl-3-phenylselenotetrahydropyran as the minor product. Lewis bases facilitate the reaction by strong hydrogen bonds between the alcoholic hydrogen and nitrogen of an additive moiety, and they stabilize the product complexes. Since the formation of the tetrahydrofuran derivative requires higher activation energy, but is thermodynamically more stable than the tetrahydropyran, it was concluded that the phenylselenoetherification reaction of linalool is thermodynamically controlled. © 2014 Springer-Verlag Wien.
URI: https://scidar.kg.ac.rs/handle/123456789/12333
Type: article
DOI: 10.1007/s00706-014-1226-5
ISSN: 0026-9247
SCOPUS: 2-s2.0-84904261804
Appears in Collections:Faculty of Science, Kragujevac
Institute for Information Technologies, Kragujevac

Page views(s)

183

Downloads(s)

4

Files in This Item:
File Description SizeFormat 
PaperMissing.pdf
  Restricted Access
29.86 kBAdobe PDFThumbnail
View/Open


Items in SCIDAR are protected by copyright, with all rights reserved, unless otherwise indicated.