Nickel-Catalyzed Ketone Formation Via Reductive Coupling Of Aryl Acids With Alkyl Halidies And Allylation Of Tertiary Alkyl Halides With Allylic Carbonates

This paper elaborates C-C bond formation via nickel-catalyzed coupling reactions based on alkyl halides. It consists of two projects: Alkyl-Aryl ketone synthesis via Ni-catalyzed reductive coupling of alkyl haides with aryl acids, Ni-catalyzed reductive allylation of unactivated tertiary alkyl halides with allylic carbonates.(1) Alkyl-aryl ketone synthesis via Ni-catalyzed reductive coupling of alkyl halides with aryl acids: This work highlights a much improved method for the construction of alkyl-aryl ketones by significantly reducing the catalyst, ligands and acid loading under the mild and easy-to-handle reaction conditions. Both secondary alkyl bromides and iodides can be incorporated. In addition, this method is applicable to α-selective synthesis of potentially bioactive aroyl C-glycosides compounds by direct reductive coupling of 1-glycosyl bromides with aryl acid derivatives, which avoids otherwise difficult multistep conversions.(2) Ni-catalyzed reductive allylation of unactivated tertiary alkyl halides with allylic carbonates: This work emphasizes a mild Ni-catalyzed reductive allylation of unactivated tertiary alkyl halides with allylic carbonate to generate C(sp3)-C(sp3) quaternary carbon products. The reaction conditions display excellent functional group tolerance, and provide products in moderate to excellent yields. It is worth noting that no isomerization of tertiary alkyl groups was observed which is often found in arylation and acylation of the tertiary electrophiles.