Molybdenum-Catalyzed Intermolecular Deoxygenative Cross-Coupling Reactions of 1,2-Diketones with a-Ketoamides

Here we describe the Mo-catalyzed intermolecular deoxygenative cross coupling of the bench stable and readily accessible1,2-diketones with alpha-ketoamides, in which three of the four carbonyl oxygen atoms were eliminated along with the formations of a carbon-nitrogen bond and a carbon-carbon double bond in one step under Mo-catalysis. Various pyrrol-2-ones were secured in up to 96% yield by utilizing a commercial Mo-catalyst. The synthetic potential of the current methodology is additionally demonstrated by synthetic transformations, a gram-scale synthesis, and derivatization of several natural products and drug molecules. The preliminary mechanistic investigation suggest this cascade process might be initiated via the formal intermolecular N-H insertion and followed by the intramolecular carbonyl- carbonyl olefination reaction, in which both steps were catalyzed by a single Mo-catalyst.

Automated summary

We describe a molybdenum-catalyzed intermolecular deoxygenative cross coupling method, in which three out of four carbonyl oxygen atoms in stable and readily accessible 1,2-diketones are eliminated, and a carbon-nitrogen bond and a carbon-carbon double bond are formed in a one-step reaction. Various pyrrol-2-ones can be synthesized with up to 96% yield using a commercial molybdenum catalyst. The potential of this method is demonstrated through synthetic transformations, gram-scale synthesis, and derivatization of natural products and drug molecules. Preliminary mechanistic investigation suggests that this cascade process may be initiated by a formal intermolecular N-H insertion reaction followed by an intramolecular carbonyl-carbonyl olefination reaction, both catalyzed by a single molybdenum catalyst.