Palladium-Catalyzed Intermolecular Acylative Heck Reactions with Imides as Acyl Electrophiles

We disclose palladium-catalyzed, intermolecular, acylative Heck reactions that use imides as acyl electrophiles. The catalyst generated from [Pd(allyl)Cl](2) and DPEphos promotes the reaction between N-benzoylglutarimides and norbornene in the presence of silver phosphate. The acylative Heck reaction encompasses an array of N-benzoylglutarimide electrophiles that contain electron-donating, halogenated, and electron-withdrawing substituents to generate alpha,beta-unsaturated ketones in moderate to high yields (25-82%). The bicylic alpha,beta-unsaturated ketones are readily transformed into polycyclic architectures via thermal hetero-Diels-Alder reactions that occur by the dimerization of the alpha,beta-unsaturated ketones.

Automated summary

In this study, a novel palladium-catalyzed reaction was disclosed using imides as acyl electrophiles to prepare a series of polycyclic compounds. The reaction achieved moderate to high yields of α,β-unsaturated ketones, which were readily transformed into polycyclic architectures via thermal hetero-Diels-Alder reactions.