Ligand-controlled non-decarbonylative and decarbonylative conversions of acyl fluorides were developed using a Pd(OAc)/EtSiH combination. When tricyclohexylphosphine (PCy) was used as the ligand, aldehydes were obtained as simple reductive conversion products. The use of 1,2-bis(dicyclohexylphosphino)ethane (CyP(CH)PCy, DCPE) as the ligand, however, favored the formation of hydrocarbons, which are decarbonylative reduction products.

The first palladium‐catalyzed construction of ketones through Suzuki–Miyaura reaction by using acid fluorides is described. In contrast to typical acyl electrophiles such as acid chlorides, acid fluorides are uncommon acyl electrophiles to use in boron‐based coupling reactions, probably due to a high level of stability toward nucleophiles. This first attempt to use acid fluorides as a coupling partner with boronic acids allowed highly functional group tolerance and a wide substrate scope while affording various ketones in effective yields.

Ap alladium-catalyzed annulation of acyl fluorides with norbornene is described. This study reports the first example of an annulationo fa cyl fluorides in the presence of a transition-metal catalyst. Polycyclic ketones are obtained from the cleavage of the CÀFa nd CÀHb onds of the acyl fluoridea nd the rearrangement of the carbonyl moiety by decarbonylation and CO reinsertion. Scheme1.Transition-metal-catalyzed CÀCbondformation reactionsofa cyl fluorides.

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