A sustainable pathway for the synthesis of tetracyclic
purinium
salts via ruthenium-catalyzed electro-oxidative annulation of C
6-arylpurine nucleosides with alkynes without
a stoichiometric metal oxidant has been developed. The protocol described
herein exhibits high regioselectivity, broad scope, and wide functional
group tolerance, allowing efficient coupling of various biologically
important molecules including acyclic, ribosyl, arabinosyl, and deoxyribosyl
purine nucleoside derivatives. A novel purinoisoquinolinium-coordinated
ruthenium(0) sandwich intermediate has been isolated, crystallographically
characterized, and electrochemically analyzed, offering direct mechanistic
insight.