標題: Theoretical Calculations for the 1,4-Hydrogen Shift of 1-Hydroxyallyl Radicals Leading to alpha-Keto Radicals; Prediction of Facilitation by 1-Amino and 3-Tin Substituents
作者: Matsubara, Hiroshi
Kawamoto, Takuji
Fukuyama, Takahide
Ryu, Ilhyong
應用化學系
Department of Applied Chemistry
關鍵字: DFT calculation;1-Hydroxyallyl radical;1,4-Hydrogen transfer
公開日期: 1-Sep-2018
摘要: DFT calculations were carried out to elucidate the 1,4-hydrogen shift of 1-hydroxyallyl radicals to give alpha-keto radicals. The 1,4-H shift is predicted to be exothermic with large energy barriers. However, the energy barriers of 1,4-H shift were predicted to be lowered significantly by 1-amino and 3-tin substituents. The results agreed well with the experimental results shown by the stannylcarbonylation of alkynes in the presence of an amine, in which the 1,4-H shift of substituted 1-hydroxyallyl radicals has been proposed as a key step.
URI: http://dx.doi.org/10.1246/cl.180522
http://hdl.handle.net/11536/148080
ISSN: 0366-7022
DOI: 10.1246/cl.180522
期刊: CHEMISTRY LETTERS
Volume: 47
起始頁: 1197
結束頁: 1199
Appears in Collections:Articles