Facile Synthesis of Cyanide and Isocyanides from CO

Abstract The reaction of K[N(SiMe 3 ) 2 ] with 13 CO proceeds in C 6 D 6 or THF affording K 13 CN and O(SiMe 3 ) 2 under mild conditions as confirmed by crystallographic characterization of K(18‐crown‐6)CN. Similarly reaction of the alkali metal amides, M[N(SiR 3 )R′] (M=Li, K; R=Ph, Me; R′=alkyl, aryl) provides the corresponding 13 C labeled isocyanide RN 13 C and MOSiR 3 , generally in high yields. In some instances, the use of the sterically bulky Ph 3 Si‐substituent is required to preclude 1,2‐silyl migration affording the silylcarbamoyl salt M[Me 3 SiC(O)NR′]. These reactions have been used to obtain 19 examples of 13 C labelled isocyanides, and several examples of gram scale reactions are reported. The mechanism of the reactions is probed via reliable DFT calculations.