Nitrogen can be used as a template for C–C bond formation by the cyclization of tethered reactive groupings. The nitrogen atom can be subsequently excised by a deaminative ring-contraction reaction. Accordingly, we developed methods to achieve iterative C–N bond cleavage and C–C bond forming events from tertiary amine substrates. We discovered trimethylphosphate as a Ni-compatible reagent for the <i>in situ</i> methylation (activation) of tertiary amines. The generated ammonium intermediates undergo Ni-catalyzed C–N bond cleavages and subsequent functionalization. In advanced applications, we demonstrate how the nitrogen atom within a tertiary amine can be viewed as a template for successive C–C bond forming reactions. A novel deaminative ring-contraction reaction will be discussed.

Methods for iterative group transfer from nitrogen and tertiary amine-templated strategies for the synthesis of polycyclic aromatics

ACS Fall 2021

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