Dearomatization of Unactivated Arenes via Catalytic Hydroalkylation
Kelly A. McDaniel, Anna R. Blood, Gavin C. Smith, Nathan T. Jui
Abstract
The dearomative cyclization of linear amides to complex spirocyclic butyrolactams has been enabled by photoredox catalysis through a reductive radical-polar crossover mechanism. This mechanism operates with precision on unactivated aromatic substrates to give a wide range of 1,4-hydroalkylation products. This method utilizes a simple organic catalyst/reductant pair to deliver products in a highly flexible manner with respect to substitution, and the products can be further functionalized under simple conditions to afford a collection of motifs. The mechanistic analysis performed here outlines the salient features of this strategy, which were applied to prepare a collection of complex scaffolds including the anticonvulsive agent gabapentin.