New formation mechanism of allylic trithiocarbonates from sodium O-(2-Alkenyl) dithiocarbonates via sequential pericyclic reactions: Density functional theory study.
Density functional theory (DFT) calculations at the B3LYP/6-31G(d) level demonstrated that sodium O-(3-phenylallyl) dithiocarbonate undergoes [3,3]-sigmatropic rearrangement to sodium S-(1-phenylallyl) dithiocarbonate, which then isomerizes to the more thermodynamically stable sodium S-(3-phenylallyl) dithiocarbonate. The calculations also showed that sodium 2-alkenyl trithiocarbonates and their esters are more labile towards the allylic rearrangement.
Tokai University, Minami-Aso, Kumamoto, Japan.
Masashi
M
Eto
Koki
K
Yamaguchi
Yasuyuki
Y
Yoshitake
Kazunobu
K
Harano
D000475:Alkenes / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D011789:Quantum Theory; D013438:Sulfhydryl Compounds / Q000737:chemistry; D013816:Thermodynamics; D013871:Thiones / Q000737:chemistry*
D000475:Alkenes; D013438:Sulfhydryl Compounds; D013871:Thiones; C013321:trithiocarbonic acid