(3+2)-Cycloadditions of Levoglucosenone (LGO) with Fluorinated Nitrile Imines Derived from Trifluoroacetonitrile: An Experimental and Computational Study

被引：0
|
作者：
Mloston, Grzegorz [1 ]
Urbaniak, Katarzyna [1 ]
Palusiak, Marcin [2 ]
Witczak, Zbigniew J. [3 ]
Wuerthwein, Ernst-Ulrich [4 ,5 ]
机构：
[1] Univ Lodz, Fac Chem, Dept Organ & Appl Chem, Tamka 12, PL-91403 Lodz, Poland
[2] Univ Lodz, Fac Chem, Dept Phys Chem, Pomorska 163-165, PL-90236 Lodz, Poland
[3] Wilkes Univ, Nesbitt Sch Pharm, Dept Pharmaceut Sci, 84 W South St, Wilkes Barre, PA 18766 USA
[4] Univ Munster, Organ Chem Inst, Corrensstr 40, D-48149 Munster, Germany
[5] Univ Munster, Ctr Multiscale Theory & Computat CMTC, Corrensstr 40, D-48149 Munster, Germany
来源：
MOLECULES | 2023年 / 28卷 / 21期
关键词：
levoglucosenone; nitrile imines; (3+2)-cycloadditions; fluoroalkylated pyrazoles; DFT calculations; 3+2 CYCLOADDITION; 1,3-DIPOLAR CYCLOADDITION; PYRAZOLES; CELLULOSE; DERIVATIVES; ACTIVATION; ENERGY;
D O I：
10.3390/molecules28217348
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：
The in situ-generated N-aryl nitrile imines derived from trifluoroacetonitrile smoothly undergo (3+2)-cycloadditions onto the enone fragment of the levoglucosenone molecule, yielding the corresponding, five-membered cycloadducts. In contrast to the 'classic' C(Ph),N(Ph) nitrile imine, reactions with fluorinated C(CF3),N(Ar) analogues lead to stable pyrazolines in a chemo- and stereoselective manner. Based on the result of X-ray single crystal diffraction analysis, their structures were established as exo-cycloadducts with the location of the N-Ar terminus of the 1,3-dipole at the alpha-position of the enone moiety. The DFT computation demonstrated that the observed reaction pathway results from the strong dominance of kinetic control over thermodynamic control.
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页数：15
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