(E)-α,β-unsaturated amides from tertiary amines, olefins and CO via Pd/Cu-catalyzed aerobic oxidative N-dealkylation

Abstract

A novel Pd/Cu-catalyzed chemoselective aerobic oxidative N-dealkylation/carbonylation reaction has been developed. Tertiary amines are utilized as a "reservoir" of "active" secondary amines in this transformation, which inhibits the formation of undesired by-products and the deactivation of the catalysts. This protocol allows for an efficient and straightforward construction of synthetically useful and bioactive (E)-α,β-unsaturated amide derivatives from easily available tertiary amines, olefins and CO.

Difluorocarbene-Based Cyanation of Aryl Iodides

“…11b,c Because of its strong oxidizing power, Cu II can be readily reduced to Cu I in the reaction system. 32 The coordination of a ligand and CNgives the Cu I CN complex D. Oxidative insertion of CuI into the Ar-I bond delivers ArCu III CN (intermediate E), reductive elimination from which affords the final product. Although the last reductive elimination also releases the catalyst Cu I , a stoichiometric amount of the Cu II source is still necessary, probably because the reductive elimination proceeds quite slowly and/or the Cu I is deactivated by coordinating ligands.…”

Recent Advances in the Functionalization of Hydrocarbons: Synthesis of Amides and its Derivatives

“…reported a novel and straightforward palladium/copper‐catalyzed strategy for the synthesis of ( E )‐α,β‐unsaturated amide derivatives from olefins, tertiary amines, and carbon monoxide that employed the combination of PdCl 2 (PPh 3 ) 2 and Cu(OAc) 2 . H 2 O system as a catalyst and O 2 as the terminal oxidant in the mixture of toluene and DMSO (Scheme a) . This reaction proceeded through the activation of the C−N bond of tertiary amines and subsequent carbonylation reaction.…”

Metal‐Free One‐Pot Three‐Component Synthesis of Quinazoline Derivatives via Peroxide‐Mediated Direct Oxidative Amination of C(sp3)–H Bonds

“…Most of the known examples rely on the use of transition metals or iodine‐based catalysts . Notably, numerous reagents have been used as a C1 synthon for the synthesis of nitrogen‐containing compounds, including DMF, DMSO, CH 3 OH, CO 2 , CO, tertiary aliphatic amine, dimethylcarbonate, N , N ‐dimethylaniline, and N , N ‐dimethylethanolamine . Additionally, the use of abundant and inexpensive ammonia and ammonium salts as an ideal nitrogen source for the synthesis of nitrogen‐containing organic molecules has recently attracted significant interests …”