(3+2)-Cycloadditions of Levoglucosenone (LGO) with Fluorinated Nitrile Imines Derived from Trifluoroacetonitrile: An Experimental and Computational Study-Reference-Cited by-同舟云学术

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

Published:2023-10-30 Issue:21 Volume:28 Page:7348
ISSN:1420-3049
Container-title:Molecules
language:en
Short-container-title:Molecules

Author:

Mlostoń Grzegorz¹^ORCID,Urbaniak Katarzyna¹,Palusiak Marcin²^ORCID,Witczak Zbigniew J.³,Würthwein Ernst-Ulrich⁴^ORCID

Affiliation:

1. Department of Organic & Applied Chemistry, Faculty of Chemistry, University of Lodz, Tamka 12, PL-91-403 Lodz, Poland

2. Department of Physical Chemistry, Faculty of Chemistry, University of Lodz, Pomorska 163/165, PL-90-236 Lodz, Poland

3. Department of Pharmaceutical Sciences, Nesbitt School of Pharmacy, Wilkes University, 84 W. South Street, Wilkes-Barre, PA 18766, USA

4. Organisch-Chemisches Institut and Center for Multiscale Theory and Computation (CMTC), Universität Münster, Corrensstrasse 40, D-48149 Münster, Germany

Abstract

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 α-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.

Publisher

MDPI AG

Subject

Chemistry (miscellaneous),Analytical Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Molecular Medicine,Drug Discovery,Pharmaceutical Science

Link

https://www.mdpi.com/1420-3049/28/21/7348/pdf

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