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

作者：Prakash G K Surya^*; Zhang Zhe; Wang Fang; Rahm Martin; Ni Chuanfa; Iuliucci Marc; Haiges Ralf; Olah George A

来源：Chemistry - A European Journal, 2014, 20(3): 831-838.

DOI：10.1002/chem.201303509

• fluoroalkenoates
• linear free energy relationship
• nitrone
• olefination
• substituent effects

alpha-Fluoroalkenoates and 4-fluoro-5-isoxazolidinones are of vast interest due to their potential biological applications. We now demonstrate the syntheses of (E)--fluoroalkenoates and 4-fluoro-5-isoxazolidinones by the reactions between nitrones and -fluoro--bromoacetate. By altering N-substituents in nitrones, (E)--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.

• 出版日期2014-1-13