Synfacts 2020; 16(04): 0411
DOI: 10.1055/s-0040-1707645
Metals in Synthesis
© Georg Thieme Verlag Stuttgart · New York

Palladium-Catalyzed γ-C(sp3)–H Bond Activation of Tertiary Alkyl Amines

Mark Lautens
Randy Sanichar
Rodrigalvarez J, Nappi M, Azuma H, Flodén NJ, Burns ME, Gaunt MJ. * University of Cambridge, UK
Catalytic C(sp3)–H Bond Activation in Tertiary Alkylamines.

Nat. Chem. 2020;
12: 76-81
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18. März 2020 (online)



Gaunt and co-workers report a novel ligand-enabled palladium(II)-catalyzed γ-C(sp3)–H arylation. Selective functionalization of tertiary alkyl amines is observed utilizing arylboronic acids under mild conditions. The reaction is enantioselective, with enantiotopic methyl group differentiation, allowing efficient and selective access to γ-aryl tertiary amine scaffolds.



The authors propose that the reaction proceeds by amine complexation to the palladium(II) ligand complex, followed by a concerted ligand-assisted metalation–deprotonation process to access the palladacycle. This intermediate then undergoes transmetalation with the boronic acid, which then undergoes a reductive elimination to afford the product.