Chemoselective Synthesis of Cyanoformamides from Isocyanates and a Highly Reactive Nitrile Anion Reservoir

The direct addition of a nitrile anion to isocyanates is reported for a straightforward preparation of valuable cyanoformamides. Through the proper activation of an adequate silicon‐ ate complex precursor (PhMe 2 SiCN) with a Lewis base (potassium tert‐ amylate) under Barbier‐type conditions, the cyanide was instantaneously released, thus yielding the desired motif with full chemocontrol. No particular structural restriction was noticed for engaging in the transformation a wide series of commercially available isocyanates.