Ralf Haiges - Stereoselective Synthesis of Fluoroalkenoates and Fluorinated Isoxazolidinones: N-Substituents Governing the Dual Reactivity of Nitrones.

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      Publication Details (including relevant citation   information): Prakash, G. K. Surya, Zhang, Zhe, Wang,   Fang, Rahm, Martin, Ni, Chuanfa, Iuliucci, Marc, Haiges, Ralf,   Olah, George A., Chem. - Eur. J., 2014,   20 (3), pp 831-838

      Abstract: α-Fluoroalkenoic acid derivs. and   4-fluoro-5-isoxazolidinone derivs. s are of vast interest due to   their potential biol. applications. The authors now demonstrate   the syntheses of (E)-α-fluoroalkenoates and   4-fluoro-5-isoxazolidinones by a reaction between nitrones and   α-fluoro-α-bromoacetate. By altering N-substituents in nitrones,   (E)-α-fluoroalkenoates and 4-fluoro-5-isoxazolidinones can be   achieved, resp., with high chemoselectivity and   stereoselectivity. Exptl. and computational studies were   conducted to elucidate the reaction mechanism. Linear free energy   relationship studies further revealed that the N-substituent   effects are primarily of electronic origin. The synthesis of the   target compds. was achieved using nitrones (amine oxides) as   reactants [such as N-[(4-fluorophenyl)methylene]benzenamine   N-oxide, [N(Z)]-N-[(2E)-3-phenyl-2-propen-1-ylidene]benzenamine   N-oxide, [N(Z)]-2-methyl-N-(phenylmethylene)-2-propanamine   N-oxide,   [N(Z)]-2-methyl-N-[(2E)-3-phenyl-2-propenylidene]-2-propanamine   N-oxide] for 2-bromo-2-fluoroacetic acid Et ester. [on   SciFinder(R)]

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