Carboxylic Phosphoric Anhydrides as a New Coupling Partner in Pd-Catalyzed Coupling Reactions: A New Ketone Synthesis

Abstract

The Pd-catalyzed cross-coupling reactions of carboxylic phosphoric anhydrides with organoboronic acids or organostannanes afforded the corresponding ketones. The intramolecular Heck reaction was successful with carboxylic phosphoric anhydrides as a coupling partner.

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

“…The first method is to obtain carboxylic–phosphoric anhydrides from acyl chlorides and hydrogen phosphates under the action of stoichiometric amount of silver oxide, 20 and the second method is to obtain carboxylic–phosphoric anhydrides by carboxylic acids and phosphites under the promotion of equivalent copper oxide. 21 Although various carboxylic acid derivatives have been widely used as electrophiles in cross-coupling reactions, 22,23 transition-metal-catalyzed cross-coupling reactions of carboxylic–phosphoric anhydrides have hardly been explored. 24 For the activation of aryl anhydride catalyzed by transition metals, transition metals can randomly inserted into the C(O)–O bonds connected to oxygen atoms on both sides.…”

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

“…Since its discovery, the Heck reaction has been used as a key method to construct C–C bonds in a variety of molecular architectures. , Heck-type reactions now encompass a range of electrophiles that can be coupled to a variety of alkenes. − Of particular interest to our laboratory are acylative Heck reactions that can be leveraged to rapidly generate α,β-unsaturated ketones . In 1985, Negishi and co-workers reported the intramolecular acylative Heck reaction of ortho -allylbenzoyl chloride using stoichiometric amounts of palladium .…”