Energetic Aspects and Molecular Mechanism of 3-Nitro-substituted 2-Isoxazolines Formation via Nitrile N-Oxide [3+2] Cycloaddition: An MEDT Computational Study

被引:14
作者
Dresler, Ewa [1 ]
Wroblewska, Aneta [2 ]
Jasinski, Radomir [3 ]
机构
[1] Lukasiewicz Res Network, Inst Heavy Organ Synth Blachown, Energetykow 9, PL-47225 Kedzierzyn Kozle, Poland
[2] Univ Lodz, Dept Organ Chem, Tamka 12, PL-91403 Lodz, Poland
[3] Cracow Univ Technol, Inst Organ Chem & Technol, Warszawska 24, PL-31155 Krakow, Poland
关键词
3+2] cycloaddition; isoxazolines; Gibbs free energy of activation; Gibbs free energy of reaction; 1,3-DIPOLAR CYCLOADDITIONS; REACTIVITY; STEPWISE; SPECTROSCOPY; DERIVATIVES; ISOMERS;
D O I
10.3390/molecules29133042
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
Regioselectivity and the molecular mechanism of the [3+2] cycloaddition reaction between nitro-substituted formonitrile N-oxide 1 and electron-rich alkenes were explored on the basis of the wb97xd/6-311+G(d) (PCM) quantum chemical calculations. It was established that the thermodynamic factors allow for the formation of stable cycloadducts along all considered models. The analysis of the kinetic parameters of the main processes show that all [3+2] cycloadditions should be realized with full regioselectivity. In all cases, the formation of 5-substituted 3-nitro-2-isoxazolidines is clearly preferred. It is interesting that regiodirection is not determined by the local electrophile/nucleophile interactions but by steric effects. From a mechanistic point of view, all considered reactions should be treated as polar, one-step reactions. All attempts to locate the hypothetical zwitterionic intermediates along the cycloaddition paths were, however, not successful.
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页数:15
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