The regioselective functionalization of 7-azaindole by controlled annular isomerism employing ad irected metalation-group migration is reported. The N7 carbamoyl azaindoles undergo regioselective metalation and quenchingwith an electrophile to furnish C6-substituted derivatives which, in the presence of ac atalytic amount of ClCONR 2 promotes ac arbamoyl group shift or dance from N7 to N1. As econd directed metalation/electrophile quench sequence leads to 2,6substituted azaindoles.O ptimization of the metalation conditions for C2 and C6, separately and iteratively,i sp resented. Using the directed metalation group dance strategy,alate-stage deuteration of an antipsychotic drug is described. Overall, the controlled migration of the carbamoyl directing group allows multiple functionalization events of the bioactive azaindole scaffold.Azaindoles occupy ap rominent position in drug discovery research because of their diverse bioactivities,e specially in protein kinase inhibition for the development of anticancer therapies.Among the four isosteres,the 7-azaindole scaffold, also present in arare class of natural products, [1] has emerged as the key heterocycle for structural modification towards new bioactive molecules ( Figure 1A). [2] Among the synthetic routes for 7-azaindoles,metalation-based methodologies have achieved dominance over classical processes because of the advantages of regioselectivity,m ultiple substitution, and ready modification of the prototype nucleus. [3,4] In previous efforts,w ed emonstrated the power of the directed ortho metalation (DoM) reaction in new halogen-dance strategies, [5] anionic ortho-Fries rearrangement processes, [6] latent directed metalation group (DMG) protocols, [7] and, as demonstrated on the 7-azaindole framework, walk-around-the-ringsequences. [4a,b,8] Whilst synthetically powerful, these metalationbased approaches involve several steps:D MG introduction, its use to direct the functionalization event, and its subsequent removal or modification.

The regioselective functionalization of 7‐azaindole by controlled annular isomerism employing a directed metalation‐group migration is reported. The N7 carbamoyl azaindoles undergo regioselective metalation and quenching with an electrophile to furnish C6‐substituted derivatives which, in the presence of a catalytic amount of ClCONR2 promotes a carbamoyl group shift or dance from N7 to N1. A second directed metalation/electrophile quench sequence leads to 2,6‐substituted azaindoles. Optimization of the metalation conditions for C2 and C6, separately and iteratively, is presented. Using the directed metalation group dance strategy, a late‐stage deuteration of an antipsychotic drug is described. Overall, the controlled migration of the carbamoyl directing group allows multiple functionalization events of the bioactive azaindole scaffold.