Quantum chemical study on the mechanism and selectivity of [3+2] cycloaddition reactions of aryl nitrile oxides with furanone

被引:5
|
作者
Abdullah, Harun [1 ]
Opoku, Ernest [1 ]
机构
[1] Nesvard Inst Mol Sci, Dept Mol Quantum Chem, Accra, Ghana
关键词
DFT calculations; 3+2] cycloadditions; GEDT; Chemoselectivity; Nitrile oxide; 1,3-DIPOLAR CYCLOADDITION; REACTIVITY; AZIDES;
D O I
10.1007/s00214-022-02915-4
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The mechanism, regio-, chemo-, diastereo-, stereo- and enantio-selectivity of the [3 + 2] cycloaddition reaction of aryl nitrile oxides with 5-acetoxy-2(5H)-furanone has been performed by means of several computational approaches, namely, activation and reaction energies, global electron density transfer (GEDT), DFT reactivity indices and rate constants. The titled reaction leads to formation of 2-isoxalines which are important intermediates for the construction of many synthetically important cycloadducts. The calculations were performed using hybrid density functionals M06-2X, B3LYP and MPWB1K together with split valence triple zeta basis set 6-311++ G(d,p). Chemo- and regio-selectivity is not affected by the nature of substituent on the aryl nitrile oxides. IRC calculations and activation energies show that this reaction follows an asynchronous concerted mechanism. Analysis of the electrophilic P-A(+) and nucleophilic P-A(-) Parr functions at the different reaction sites in the 5-acetoxy-2(5H)-furanone indicates that the aryl nitrile oxides add across the atomic centers with the highest Mulliken atomic spin densities. The results reported herein are in good agreement with previous experimental works. The GEDT calculations unravel the low polar character of the [3 + 2] cycloaddition reactions. Overall, the viability of these [3 + 2] cycloaddition reactions depends on the low polar character, which also depends on the electrophilic and nucleophilic character of the reacting 5-acetoxy-2(5H)-furanone and aryl nitrile oxides, respectively.
引用
收藏
页数:14
相关论文
共 50 条
  • [21] How Different Are Nitrile Oxides from Nitrones in zw-type [3+2] Cycloaddition Reactions? A Molecular Electron Density Theory Study
    Domingo, Luis R.
    Perez, Patricia
    JOURNAL OF ORGANIC CHEMISTRY, 2025,
  • [22] Regio- and Stereoselective (3+2)-Cycloaddition of Nitrile Oxides and Nitrones to N-Vinylindole
    Efremova, M. M.
    Kostikov, R. R.
    Larina, A. G.
    Molchanov, A. P.
    RUSSIAN JOURNAL OF ORGANIC CHEMISTRY, 2017, 53 (02) : 246 - 250
  • [23] [3+2] cycloaddition of 1-(4-Methoxybenzyl)indoles and azaindoles with nitrile oxides
    Kimura, Reina
    Sato, Yoshihiro
    Morisaki, Kazuhiro
    Nishi, Takahide
    TETRAHEDRON, 2022, 113
  • [24] A highly efficient [3+2] cycloaddition of nitrile oxides and azomethine imines to N-vinylpyrroles
    Efremova, Mariia M.
    Molchanov, Alexander P.
    Stepakov, Alexander V.
    Kostikov, Rafael R.
    Shcherbakova, Victoriya S.
    Ivanov, Andrey V.
    TETRAHEDRON, 2015, 71 (14) : 2071 - 2078
  • [25] The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3+2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study
    Zawadzinska, Karolina
    Rios-Gutierrez, Mar
    Kula, Karolina
    Wolinski, Przemyslaw
    Miroslaw, Barbara
    Krawczyk, Tomasz
    Jasinski, Radomir
    MOLECULES, 2021, 26 (22):
  • [26] Understanding the reactivity and regioselectivity of [3+2] cycloaddition reactions between substituted nitrile oxides and methyl acrylate. A molecular electron density theory study
    Ndassa, Ibrahim Mbouombouo
    Adjieufack, Abel Idrice
    Ketcha, Joseph Mbadcam
    Berski, Slawomir
    Rios-Gutierrez, Mar
    Domingo, Luis R.
    INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 2017, 117 (24)
  • [27] The role of the polarity on the mechanism and selectivity in the [3+2] cycloaddition reaction between CF3-ynone ylide and azide group: A quantum chemical investigation
    Benallou, Abdelilah
    Lakbaibi, Zouhair
    Garmes, Hocine
    El Abdallaoui, Habib El Alaoui
    JOURNAL OF FLUORINE CHEMISTRY, 2019, 219 : 79 - 91
  • [28] [3+2] Cycloaddition reactions of nitrile oxides generated in situ from aldoximes with alkenes and alkynes under ball-milling conditions
    Fang, Run-Kai
    Yin, Zheng-Chun
    Chen, Jun-Shen
    Wang, Guan-Wu
    GREEN CHEMISTRY LETTERS AND REVIEWS, 2022, 15 (03) : 519 - 528
  • [29] Experimental and Theoretical MEDT Study of the Thermal [3+2] Cycloaddition Reactions of Aryl Azides with Alkyne Derivatives
    Ben El Ayouchia, Hicham
    Lahoucine, Bahsis
    Anane, Hafid
    Rios-Gutierrez, Mar
    Domingo, Luis R.
    Stiriba, Salah-Eddine
    CHEMISTRYSELECT, 2018, 3 (04): : 1215 - 1223
  • [30] [3+2] Cycloaddition of nitrile oxides to dichloropropenes and 1,3-dichlorobut-2-ene: A regioselectivity issue
    Shilova, Alexandra N.
    Shatokhina, Nina S.
    Kondrashov, Evgeniy V.
    JOURNAL OF HETEROCYCLIC CHEMISTRY, 2024, 61 (04) : 556 - 567