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

• Published in: Journal of organic chemistry 2021-05, Vol.86 (9), p.6863-6868
• Main Authors: Kadam, Abhishek A, Metz, Tanner L, David, Colton M, Koeritz, Mason T, Stanley, Levi M
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.1c00087

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 α,β-unsaturated ketones in moderate to high yields (25–82%). The bicylic α,β-unsaturated ketones are readily transformed into polycyclic architectures via thermal hetero-Diels–Alder reactions that occur by the dimerization of the α,β-unsaturated ketones.