We wish to report on a) the unusual peri(C-4)metalation reactivity of N-unprotected 7-azaindole 3-DMG (1 in below scheme) dianion frameworks using a new anionic shielding C-2 protection concept (2 ) and its generalization for the synthesis of 4 substituted derivatives, b) the use of the thereby derived powerful C-4 CONEt2 DMG for further DoM leading via Suzuki cross-coupling and directed remote metalation (DreM) chemistries, to new annulated heterocyclic systems and c) the use of a ring-walk metalation platform for the regioselective construction of polysubstituted 7-azaindoles (3 ). The reported results constitute, to the best of our knowledge, the first observation of peri-metalation of CONEt2 and SO2NEt2 DMG system. Figure 1. <img src='https://acs-archive-assets2.s3.amazonaws.com/239nm/uploads/12480_figure.jpg' alt='' /> 1. J. J. Song, J. T. Reeves, F. Gallou, Z. Tan, N. K. Yee, C. H. Sennayake, Chem. Soc. Rev. 2007, 36, 11202. T. Fukuda, H. Akashima, M. Iwao, Tetrahedron 2005, 61, 68893. M. Iwao, Heterocycles 1993, 36, 29

In situ anionic shielding for regioselective metalation: Directed peri-metalation and iterative
functionalization routes to polysubstituted 7-azaindoles

243rd National Meeting (2012)

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In situ anionic shielding for regioselective metalation: Directed peri-metalation and iterative functionalization routes to polysubstituted 7-azaindoles