Exploring the scope of nitriles (Scheme 2b) required to identify a suitable solvent other than acetonitrile. After extensive screening (see SI for details; Table .10 and S2.11), we found that nitromethane would allow the coupling of aliphatic nitriles bearing different carbon chains with phenylacetylenes to provide the corresponding 2,3,6-trisubstituted pyridines (3o-3t, Scheme 2b). Nitriles having a halogen atom at the terminal position were also found to be suitable and afforded the respective pyridine derivatives 3u, 3v (confirmed by single crystal X-ray analysis) and 3w; however, competitive reduction to 3a was observed for the latter. Nitriles with a vinylic and allylic double bond were converted to the pyridine derivatives 3x and 3y. The lower yields might be explained by a competing radical cyclization of the intermediate arene radical onto the alkene double bond, and indeed, such a process was confirmed with the isolation of 3x' that was formed along with 3x. Deuterated acetonitrile (CD3CN) afforded d3-3a in good yield with no observable erosion of the deuterium incorporated. However, no product formation was observed if aromatic nitriles were employed.