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Stereoselective Synthesis of Fluoroalkenoates and Fluorinated Isoxazolidinones: N‐Substituents Governing the Dual Reactivity of Nitrones
Author(s) -
Prakash G. K. Surya,
Zhang Zhe,
Wang Fang,
Rahm Martin,
Ni Chuanfa,
Iuliucci Marc,
Haiges Ralf,
Olah George A.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201303509
Subject(s) - stereoselectivity , reactivity (psychology) , chemistry , dual (grammatical number) , stereochemistry , organic chemistry , catalysis , philosophy , medicine , alternative medicine , pathology , linguistics
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.