Regioselective Conjugate Addition of Nitriles to α,β‐Unsaturated Imines: Synthesis of Fluorinated Primary Enamines and 2‐Aminopyridine Derivatives

The regioselective Michael addition of the carbanion of 2‐phenylacetonitrile (R 2 = Ph) and malononitrile (R 2 = CN) to fluoroalkylated α,β‐unsaturated imines 1 is described. Fluorinated imines 1 were used as intermediates for the regioselective 1,4‐addition and synthesis of functionalized fluorinated primary enamines 5 and 7 , fluorine‐containing trans ‐3,4‐dihydro‐2‐aminopyridines 2 , and fluorinated 2‐aminopyridines 4 and 8 , which were obtained with total atom economy. Derivatives 2 and 8 were also prepared by an intramolecular cyclocondensation reaction of functionalized fluorinated primary enamines 5 and 7 , respectively, in the presence of a base (NaH).