THEORETICAL STUDY OF THE REGIOSELECTIVITY OF THE ADDITION OF THE TRIPLET OXYGEN ATOM TO UNSYMMETRICAL SUBSTITUTED ALKENES

被引：3

作者：

Messaoudi, Boulanouar ^{[1
]}

Mekelleche, Sidi Mohamed ^{[1
]}

Mora-Diez, Nelaine ^{[2
]}

机构：

[1] Univ Tlemcen, Dept Chem, Lab Appl Thermodynam & Mol Modeling, Tilimsen 13000, Algeria

[2] Thompson Rivers Univ, Dept Chem, Kamloops, BC V2C 0C8, Canada

来源：

JOURNAL OF THEORETICAL & COMPUTATIONAL CHEMISTRY | 2012年 / 11卷 / 03期

关键词：

Atmospheric reactions; substituted alkenes; O(P-3) atoms; regioselectivity; ab initio calculations; RADICAL-ADDITION; REACTION-MECHANISM; AB-INITIO; HYDROGEN ADDITION; ORGANIC-COMPOUNDS; OLEFINS; REACTIVITY; ETHYLENE; FLUOROETHENES; FORMALDEHYDE;

D O I：

10.1142/S0219633612500320

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A theoretical study of the reactivity and regioselectivity of the addition of the triplet oxygen atom O(P-3) to a series of unsymmetrical substituted alkenes has been performed at the PMP2/6-311++G(d,p) level of theory. Two reaction pathways, namely, the addition to the substituted carbon atom (alpha-site) and addition to the non-substituted carbon atom ( beta-site), have been studied. Our calculations show that the beta-addition products are kinetically more favored; whereas the alpha-addition products are found to be thermodynamically more stable. The regioselectivity (alpha vs. beta) of the addition of the O(P-3) to the carbon-carbon double bond is predicted by means of the relative energies of the localized transition states and also by the calculation of spin densities of the (3)pi pi* states of reactants and Fukui indices corresponding to the radical attack to alkenes. Our calculations are in good agreement with experimental outcomes.

引用

页码：527 / 535

页数：9