Pd-Catalyzed Decarbonylative Olefination of Aryl Esters: Towards a Waste-Free Heck Reaction

Abstract

Easy and clean: A palladium(0)‐catalyzed decarbonylative Heck olefination of activated esters of aryl, heteroaryl, and vinyl carboxylic acids opens up an opportunity for a novel waste‐free Heck olefination process (see scheme).

Intramolecular Oxyacylation of Alkenes Using a Hydroxyl Directing Group

“…Increasing the steric bulk of the phosphine ligand from PCy 3 to Me-Phos, 21 X-Phos, 22 or (R)-MOP 23 did, however, increase the yield of 2a (Table 1, 2 and 12% (R)-MOP in mesitylene at 170°C afforded the oxyacylation product 2a in 78% isolated yield. The product was formed as a racemate, as determined by HPLC for enantiomer separation.…”

Synthesis of benzylpalladium complexes through C–O bond cleavage of benzylic carboxylates: Development of a novel palladium-catalyzed benzylation of olefins

“…[24], They have further expanded the method to direct conversion of carboxylic acids and olefins into olefin arylation products in the presence of a dicarbonate [25][26][27].…”

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

“…Furthermore, when intermolecular Heck reaction was attempted as shown in Scheme 6, the desired product 16 was not obtained and ethyl trans-cinnamate (17) was isolated due to decarbonylation of the acylpalladium intermediate. 12 In conclusion, we have found that the carboxylic phosphoric anhydride can be utilized as a new coupling partner in the Suzuki and Stille reactions. Intramolecular Heck reaction of the carboxylic phosphoric anhydrides was successful, whereas intermolecular Heck reaction afforded the decarbonylation product.…”