Citation: YAN Chaoxian, YANG Fan, WU Ruizhi, ZHOU Dagang, YANG Xing, ZHOU Panpan. Application of Natural Orbital Fukui Functions and Bonding Reactivity Descriptor in Understanding Bond Formation Mechanisms Underlying [2+4] and [4+2] Cycloadditions of o-Thioquinones with 1, 3-Dienes[J]. Acta Physico-Chimica Sinica, ;2018, 34(5): 497-502. doi: 10.3866/PKU.WHXB201709222 shu

Application of Natural Orbital Fukui Functions and Bonding Reactivity Descriptor in Understanding Bond Formation Mechanisms Underlying [2+4] and [4+2] Cycloadditions of o-Thioquinones with 1, 3-Dienes

Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China

Corresponding author: ZHOU Panpan, zhoupp@lzu.edu.cn
Received Date: 30 August 2017
Revised Date: 18 September 2017
Accepted Date: 18 September 2016
Available Online: 22 May 2017
Fund Project: The project was supported by the National Natural Science Foundation of China (21403097) and the Fundamental Research Funds for the Central Universities, China (lzujbky-2016-45)the Fundamental Research Funds for the Central Universities, China lzujbky-2016-45the National Natural Science Foundation of China 21403097

o-Thioquinones can undergo either [2+4] or [4+2] cycloaddition reactions with acyclic dienes. To illustrate the bonding processes in these cycloadditions, the natural orbital Fukui function (NOFF) and bonding reactivity descriptor have been employed. The electrophilicity of a bond or an orbital in the o-thioquinone as well as in the acyclic diene has been found using the NOFF, which suggests that electron transfer takes place from an electron-donating bonding orbital to an electron-accepting antibonding/bonding orbital, leading to the cyclic product via the formation of a circular loop and two covalent bonds. The bonding reactivity descriptor shows that covalent bonds readily form between atom k1 of one molecule with a large f_k1⁺ value and atom k2 of another molecule with a large f_k2^- value. Both the NOFF and the bonding reactivity descriptor are efficient tools for interpreting the mechanism underlying the [2+4] and [4+2] cycloaddition between o-thioquinones and acyclic dienes.
- Fukui function,
- Natural orbital Fukui function (NOFF),
- Bonding reactivity descriptor,
- Cycloaddition,
- Nucleophilic/electrophilic attack
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