Palladium-Catalyzed Decarbonylative Sonogashira Alkynylation of Carboxylic-Phosphoric Anhydrides.

We report the first palladium-catalyzed decarbonylative alkynylation of carboxylic-phosphoric anhydrides via highly selective C(O)-O bond cleavage. Carboxylic-phosphoric anhydrides are highly active carboxylic acid derivatives, which are generated through activating carboxylic acids using phosphates by esterification or direct dehydrogenative coupling with phosphites. Highly valuable internal alkynes have been generated by the present method, and the efficiency of this approach has been demonstrated through a wide substrate scope and excellent functional group tolerance.

Palladium-catalyzed Suzuki-Miyaura cross-coupling of carboxylic-phosphoric anhydrides via C-O bond cleavage.

A robust palladium-catalyzed Suzuki-Miyaura reaction of carboxylic-phosphoric anhydrides via highly selective C(O)-O bond cleavage under inorganic base-free conditions has been reported. Carboxylic-phosphoric anhydrides, generated through activating carboxylic acids using phosphates by esterification or direct dehydrogenative reaction with phosphites, have been employed as highly reactive electrophiles for Suzuki-Miyaura cross-coupling reactions. Broad substrate scope and excellent functional group tolerance have been demonstrated to be a general and practical approach for the synthesis of highly valuable ketones.