"Abnormal" Addition of NHC to a Conjugate Acid of CAAC: Formation of N-Alkyl-Substituted CAAC.

The addition reactions of N-heterocyclic carbenes (NHCs) are mostly known to occur through the carbenic centre (C2), which leads to a "normal" adduct. Herein, we report the "abnormal" addition of NHC 1 (1,3-(2,6-iPr C H )-imidazole-2-ylidene) to a conjugate acid of cyclic (alkyl)(amino)carbene 2 (CAAC =1-iPr-3,3,5,5-Me -pyrrolinium triflate). Mechanistic study revealed that this reaction proceeded through the in situ formation of 1,3-(2,6-iPr C H )-imidazolium cation 4 and N-iPr-substituted CAAC 5 followed by the oxidative addition of compound 5 across the C4-H bond (alias backbone C-H) of compound 4. The in situ formation of compound 5 was also proven by the oxidative addition of it to the N-H group of iPrNH . DFT calculations also supported the mechanistic findings. A different methodology for the in situ generation of compound 5 by using TMPLi is also described.