Radical Nitration-Debromination of α-Bromo-α-fluoroalkenes as a Stereoselective Route to Aromatic α-Fluoronitroalkenes-Functionalized Fluorinated Building Blocks for Organic Synthesis

Vladimir A Motornov; Vasiliy M Muzalevskiy; Andrey A Tabolin; Roman A Novikov; Yulia V Nelyubina; Valentine G Nenajdenko; Sema L Ioffe

doi:10.1021/acs.joc.7b00578

Radical Nitration-Debromination of α-Bromo-α-fluoroalkenes as a Stereoselective Route to Aromatic α-Fluoronitroalkenes-Functionalized Fluorinated Building Blocks for Organic Synthesis

J Org Chem. 2017 May 19;82(10):5274-5284. doi: 10.1021/acs.joc.7b00578. Epub 2017 May 10.

Authors

Vladimir A Motornov^{1

2}, Vasiliy M Muzalevskiy³, Andrey A Tabolin¹, Roman A Novikov^{1

4}, Yulia V Nelyubina⁵, Valentine G Nenajdenko³, Sema L Ioffe¹

Affiliations

¹ N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences , Leninsky prosp. 47, Moscow 119991, Russian Federation.
² Higher Chemical College, D. I. Mendeleev University of Chemical Technology of Russia , Miusskaya sq. 9, Moscow 125047, Russian Federation.
³ Department of Chemistry, M. V. Lomonosov Moscow State University , Leninskie Gory 1, Moscow 119992, Russian Federation.
⁴ V. A. Engelhardt Institute of Molecular Biology, Russian Academy of Sciences , Vavilov str. 32, Moscow 119991, Russian Federation.
⁵ A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov str. 28, Moscow 119991, Russian Federation.

PMID: 28448146
DOI: 10.1021/acs.joc.7b00578

Abstract

A new highly efficient method for the synthesis of 2-fluoro-2-nitrostyrenes was described. Radical nitration of readily available 2-bromo-2-fluorostyrenes with Fe(NO₃)₃·9H₂O resulted in the formation of the corresponding α-fluoro-nitroalkenes in isolated yields up to 92%. The reaction proceeded as a nitration-debromination sequence to highly stereoselectively give α-fluoro-nitroalkenes as Z-isomers only. The broad scope of this method was demonstrated. Prepared monofluorinated alkenes were shown to be versatile building blocks for the synthesis of various fluorinated products.

Publication types

Research Support, Non-U.S. Gov't