N-C Axially Chiral Compounds with an ortho-Fluoro Substituent and Steric Discrimination between Hydrogen and Fluorine Atoms Based on a Diastereoselective Model Reaction
| Autor: | Christian Roussel, Daniel Farran, Asumi Iida, Mizuki Matsuoka, Nicolas Vanthuyne, Hiroshi Hasegawa, Osamu Kitagawa |
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| Přispěvatelé: | Shibaura Institute of Technology, Tokyo University of Pharmacy and Life Sciences (TUPLS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Aix Marseille Université (AMU) |
| Rok vydání: | 2019 |
| Předmět: |
chemistry.chemical_classification
Steric effects Atropisomer 010405 organic chemistry [CHIM.ORGA]Chemical Sciences/Organic chemistry Organic Chemistry Substituent chemistry.chemical_element 010402 general chemistry 01 natural sciences Medicinal chemistry 0104 chemical sciences chemistry.chemical_compound chemistry Axial chirality Steric factor Fluorine Enantiomer Alkyl |
| Zdroj: | Journal of Organic Chemistry Journal of Organic Chemistry, American Chemical Society, 2019, 84 (6), pp.3169-3175. ⟨10.1021/acs.joc.8b03043⟩ Journal of Organic Chemistry, 2019, 84 (6), pp.3169-3175. ⟨10.1021/acs.joc.8b03043⟩ |
| ISSN: | 1520-6904 0022-3263 |
| DOI: | 10.1021/acs.joc.8b03043⟩ |
| Popis: | International audience; The fluorine atom is the second smallest atom; nevertheless, the ortho-fluoro group may lead to stable N-aryl atropisomers when the steric demand of the flanking substituents is large enough. 2-Alkyl-3-(2-fluorophenyl)quinazolin-4-ones and 3-(2-fluorophenyl)-4-methylthiazoline-2-thione were found to be the first N-aryl axially chiral compounds bearing an ortho-fluoro group whose enantiomers were isolated at ambient temperature. The reaction of alkyl halides with the anionic species prepared from 2-ethyl-3-(2-fluorophenyl)quinazolin-4-one presenting an N−C axial chirality provided a model reaction for quantitative evaluation of the steric discrimination (slight difference of steric factor) between hydrogen and fluorine atoms. In the case of low steric demand (allylation reaction) no diastereoselectivity was detected, while in the case of high steric demand (isopropylation reaction) the diastereoselectivity became significant. |
| Databáze: | OpenAIRE |
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