title: Stereoselective synthesis of fluoroalkenoates and fluorinated isoxazolidinones: N-substituents governing the dual reactivity of nitrones.
abstract: α-Fluoroalkenoates and 4-fluoro-5-isoxazolidinones are of vast interest due to their potential biological applications. We now demonstrate the syntheses of (E)-α-fluoroalkenoates and 4-fluoro-5-isoxazolidinones by the reactions between nitrones and α-fluoro-α-bromoacetate. By altering N-substituents in nitrones, (E)-α-fluoroalkenoates and 4-fluoro-5-isoxazolidinones can be achieved, respectively, with high chemo- and stereoselectivities. Experimental and computational studies have been conducted to elucidate the reaction mechanisms. Linear free energy relationship studies further revealed that the N-substituent effects are primarily of electronic origin.
authors: Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, University Park, Los Angeles, CA-90089-1661 (USA), Fax: (+1) 213-740-6679. gprakash@usc.edu.
authors: G K Surya
authors: GK
authors: Prakash
authors: Zhe
authors: Z
authors: Zhang
authors: Fang
authors: F
authors: Wang
authors: Martin
authors: M
authors: Rahm
authors: Chuanfa
authors: C
authors: Ni
authors: Marc
authors: M
authors: Iuliucci
authors: Ralf
authors: R
authors: Haiges
authors: George A
authors: GA
authors: Olah
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005461:Fluorine / Q000737:chemistry*; D054879:Halogenation; D007555:Isoxazoles / Q000138:chemical synthesis / Q000737:chemistry*; D007700:Kinetics; D008968:Molecular Conformation; D009589:Nitrogen Oxides / Q000737:chemistry*; D013237:Stereoisomerism; D013696:Temperature; D013816:Thermodynamics
chemical_list: D000475:Alkenes; D007555:Isoxazoles; D009589:Nitrogen Oxides; C015388:nitrones; D005461:Fluorine
keywords: fluoroalkenoates; linear free energy relationship; nitrone; olefination; substituent effects