Metal-free direct α-C(sp^(3))-H intramolecular cyclization of 2-alkylthiobenzoic acid in the presence of Selectfluor is described.This novel strategy provides a facile and efficient method to access important 1,3-ben...Metal-free direct α-C(sp^(3))-H intramolecular cyclization of 2-alkylthiobenzoic acid in the presence of Selectfluor is described.This novel strategy provides a facile and efficient method to access important 1,3-benzooxathiin-4-one derivatives with good functional groups tolerance and yields.展开更多
The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effect...The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effects of solvent triethylamine on these two reactions were also evaluated. It is demonstrated that path B is more preferable than path a due to low barrier height for the rate-determining step.展开更多
Reaction of diethyl 2,2-difluoro-3-（a-methylbenzyl）imino-4,4,4-trifluoropropanephosphonate （3） with triethylamine afforded a mixture of normal [1,3]-proton shift reaction product 5 and its HF-eliminated compound 6...Reaction of diethyl 2,2-difluoro-3-（a-methylbenzyl）imino-4,4,4-trifluoropropanephosphonate （3） with triethylamine afforded a mixture of normal [1,3]-proton shift reaction product 5 and its HF-eliminated compound 6Z in 1 ： 1 ratio. Upon hydrolysis, this reaction mixture gave solely 1,3,3,3-tetrafluoro-2-dioxypropanephosphonate （9）. Reaction of 3 with DBU provided only 6, in which the ratio of E/Z forms was dependent on the reaction conditions. Aqueous hydrolysis of 6 led to 9. Catalytic hydrogenation and hydrogenolysis of 6 gave geometric isomers of 11 as expected. The reaction mechanism involved was discussed.展开更多
The ab initio calculations have been performed on the reaction paths of 1,2-H shift and inversion processes of amino-carbene molecule by the Intrinsic Reaction Coordinate(IRC)method. We have determined the equilibrium...The ab initio calculations have been performed on the reaction paths of 1,2-H shift and inversion processes of amino-carbene molecule by the Intrinsic Reaction Coordinate(IRC)method. We have determined the equilibrium geometries and energies of the reactant,transition state and product,and obtained the activation energies,reaction heats,frequency factors and the activation entropies of these two reaction processes.The vibrational correlation from reactant to transition state indicated that the IRCs of 1,2-H shift and inversion processes were associated with the deformation modes of 1540 and 1208 cm^(-1),respectively.The vibrational coupling between normal coordinates in the inversion process would be helpful for selecting the inversion reaction channel.展开更多
基金the financial support from the National Natural Science Foundation of China(Nos.21572026,21702019)Advanced Catalysis and Green Manufacturing Collaborative Innovation Center,Changzhou University。
文摘Metal-free direct α-C(sp^(3))-H intramolecular cyclization of 2-alkylthiobenzoic acid in the presence of Selectfluor is described.This novel strategy provides a facile and efficient method to access important 1,3-benzooxathiin-4-one derivatives with good functional groups tolerance and yields.
文摘The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effects of solvent triethylamine on these two reactions were also evaluated. It is demonstrated that path B is more preferable than path a due to low barrier height for the rate-determining step.
基金Project supported by the National Natural Science Foundation of China （Nos. 20272075. 20372076）. Dedicated to Professor Xikui Jiang on the occasion of his 80th birthday.
文摘Reaction of diethyl 2,2-difluoro-3-（a-methylbenzyl）imino-4,4,4-trifluoropropanephosphonate （3） with triethylamine afforded a mixture of normal [1,3]-proton shift reaction product 5 and its HF-eliminated compound 6Z in 1 ： 1 ratio. Upon hydrolysis, this reaction mixture gave solely 1,3,3,3-tetrafluoro-2-dioxypropanephosphonate （9）. Reaction of 3 with DBU provided only 6, in which the ratio of E/Z forms was dependent on the reaction conditions. Aqueous hydrolysis of 6 led to 9. Catalytic hydrogenation and hydrogenolysis of 6 gave geometric isomers of 11 as expected. The reaction mechanism involved was discussed.
基金This project was supported by the National Natural Science Foundation of China.
文摘The ab initio calculations have been performed on the reaction paths of 1,2-H shift and inversion processes of amino-carbene molecule by the Intrinsic Reaction Coordinate(IRC)method. We have determined the equilibrium geometries and energies of the reactant,transition state and product,and obtained the activation energies,reaction heats,frequency factors and the activation entropies of these two reaction processes.The vibrational correlation from reactant to transition state indicated that the IRCs of 1,2-H shift and inversion processes were associated with the deformation modes of 1540 and 1208 cm^(-1),respectively.The vibrational coupling between normal coordinates in the inversion process would be helpful for selecting the inversion reaction channel.
