In this thesis, various approaches from the literature employing carbon–hydrogen bond activation for the synthesis of indoles and their close derivatives, indolines and carbazoles, have been discussed. Palladium/norbornene cooperative catalysis, in particular, presents an attractive platform for the preparation of indoles via the regioselective difunctionalization of an aryl halide and its unactivated ortho-carbon–hydrogen bond. The detailed development of a synthetic strategy for the preparation of indoles using this catalytic duo via an ortho-amination, ipso-Heck cyclization cascade is presented. Moreover, a synthesis of indolines via a modification of this strategy employing a reductive Heck cyclization is also presented, in addition to preliminary results for the enantioselective version of this transformation. Finally, an unexpected ortho-Heck reaction of aryl iodides is presented, whereupon an alkene was found to couple at the arene ortho-position, instead of the typical ipso position. An isotope labeling study was conducted, finding that the transformation was likely proceeding through an uncommon reaction pathway for palladium. The knowledge gained in these combined works is expected to help guide the development of new transformations employing palladium/norbornene cooperative catalysis.



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