Tuning the Cyclopropane Ring-Opening Reaction over Electronic Bias by Fusion to a Pre-Aromatic Ring: TfOH-Promoted Aromatization of Dibenzonorcaradienes to Dibenzo[f,h]isocoumarins

Fusion of the cyclopropane ring bearing two vicinal acceptors to the pre-aromatic dihydrophenanthrene ring, which is constructed by the Pd-catalyzed cross-coupling between the vicinal aromatic rings, is found to effectively direct the cleavage of the electronically unfavored cyclopropane bond between the vicinal acceptors. Consequently, a modular method for the rapid synthesis of dibenzo[f,h]isocoumarins from methyl ketones, aryl aldehydes, and alpha-keto esters via a reaction cascade of aldol condensation, Kukhtin-Ramirez cyclopropanation, Pd-catalyzed direct arylation, and acid-promoted aromatization has been realized.

Automated summary

A modular method for the rapid synthesis of dibenzo[f,h]isocoumarins from methyl ketones, aryl aldehydes, and alpha-keto esters has been realized by a reaction cascade of aldol condensation, Kukhtin-Ramirez cyclopropanation, Pd-catalyzed direct arylation, and acid-promoted aromatization.