A new strategy which combined Hofmann–Löffler reaction and Suzuki-Miyaura coupling was developed to harness the carbon radical by copper catalyst. The new strategy allows remote C(sp<sup>3</sup>)-H serves as a cross-coupling partner which open the gate to realize regio and enantio selective C(sp<sup>3</sup>)-H bond activation transformations. This approach enables selective δ C-H (hetero)arylation of sulfonamides via intramolecular hydrogen atom transfer (HAT) by an N-centered radical. The tranformation is both initiated and terminated by a Cu catalyst, which enables incorporation of arenes and heteroarenes by cross-coupling with boronic acids. The broad scope and utility of this catalytic method for δ C-H arylation is shown, along with mechanistic probes for selectivity of the HAT mechanism. A catalytic, asymmetric variant is also also presented, as well as a method for accessing 1,1-diaryl-pyrrolidines via iterative δ C-H functionalizations.

δ C−H (hetero)arylation via Cu-catalyzed radical relay

2019 Spring National Meeting

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