Mechanism and regioselectivity of 1,3-dipolar cycloaddition reactions of sulphur-centred dipoles with furan-2,3-dione: A theoretical study using DFT

Journal of Chemical Sciences

Ehsan Zahedi¹  Safa Ali-Asgari¹  Saeed Reza Emamian1¹ 

[1] Chemistry Department, Shahrood Branch, Islamic Azad University, Shahrood 36199-43189, Iran$$

关键词: 1;    3-Dipolar cycloaddition;    sulphur-centred 1;    3-dipoles;    regioselectivity;    DFT reactivity indices;    FMO theory.;   

DOI  :  

来源: Indian Academy of Sciences

【 摘 要 】

The mechanism and regioselectivity of 1,3-dipolar cycloaddition reactions of sulphur-centred 1,3-dipoles including thiocarbonyl S-imide (D1), thiocarbonyl S-oxide (D2) and thiocarbonyl S-sulphide (D3) with an electron-deficient dipolarophile, furan-2,3-dione (DPh), were studied in the light of some theoretical approaches, namely, activation energy, density functional theory (DFT) reactivity indices and Houk’s rule based on the frontier molecular orbital (FMO) theory at the B3LYP/6-311++G∗∗ level. The present analysis reveals that the cycloaddition reactions under study can be classified in the normal electron demand category. An excellent agreement was observed between the kinetic results and the electronic approaches; in fact, maximum hardness principle (MHP), Chattaraj’s polar model, Houk’s rule and the Gazquez-Mendez rule confirm the resultant regioselectivity based on the calculated activation energies.

【 授权许可】

Unknown