Copper-catalyzed [3 + 2]-cycloaddition of α-halonitroalkenes with azomethine ylides: facile synthesis of multisubstituted pyrrolidines and pyrroles.

An efficient route for the synthesis of multifunctionalized pyrrolidines based on copper-catalyzed diastereoselective [3 + 2]-cycloaddition of nitroalkenes with azomethine ylides was developed. Novel fluorinated heterocycles - β-fluoro-β-nitropyrrolidines - were accessed via this method. The products can be prepared in good to excellent yields and with high diastereoselectivity.

Copper-mediated oxidative [3 + 2]-annulation of nitroalkenes and pyridinium imines: efficient synthesis of 3-fluoro- and 3-nitro-pyrazolo[1,5-a]pyridines.

An efficient route to pyrazolo[1,5-a]pyridines by Cu(OAc)2-promoted oxidative [3 + 2]-annulation of nitroalkenes with in situ generated pyridinium imines is developed. The reaction with α-fluoronitroalkenes enables the first preparative synthesis of 3-fluoro-pyrazolo[1,5-a]pyridines. Cycloaddition with α-unsubstituted nitroalkenes provides access to 3-nitro-pyrazolo[1,5-a]pyridines in excellent yields.

Copper-mediated oxidative [3 + 2]-annulation of nitroalkenes and pyridinium ylides: general access to functionalized indolizines and efficient synthesis of 1-fluoroindolizines.

A general method for the synthesis of substituted indolizines by copper(ii) acetate-promoted oxidative [3 + 2]-annulation of α-fluoronitroalkenes with in situ generated pyridinium ylides was developed. Application of the copper(ii) acetate-2,6-lutidine system provides efficient access to various 1-fluoroindolizines in up to 81% yield. Both electron-rich and electron-deficient nitroalkenes as well as different pyridinium and isoquinolinium salts can be involved in the reaction.

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

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(NO)·9HO 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.