Room-Temperature Cu(II) Radical-Triggered Alkyne C-H Activation

A dimeric Cu(II) complex [Cu(II)(2)L-2(mu(2)-Cl)Cl] (1) built from an asymmetric tridentate ligand (2-(((2-aminocyclohexyl)imino)methyl) -4,6-di-tert-butylphenol) and weakly coordinating anions has been synthesized and structurally characterized. In dichloromethane solution, 1 exists in a monomeric [Cu(II)LCl] (1') (85%)-dimeric (1) (15%) equilibrium, and cyclic voltammetry (CV) and electron paramagnetic resonance (EPR) studies indicate structural stability and redox retention. Addition of phenylacetylene to the CH2Cl2 solution populates 1' and leads to the formation of a transient radical species. Theoretical studies support this notion and show that the radical initiates an alkyne C-H bond activation process via a four-membered ring (Cu(II)-O center dot center dot center dot H-C-alkyne) intermediate. This unusual C-H activation method is applicable for the efficient synthesis of propargylamines, without additives, within 16 h, at low loadings and in noncoordinating solvents including late-stage functionalization of important bioactive molecules. Single-crystal X-ray diffraction studies, postcatalysis, confirmed the framework's stability and showed that the metal center preserves its oxidation state. The scope and limitations of this unconventional protocol are discussed.

Automated summary

A dimeric Cu(II) complex was synthesized and characterized, showing a monomeric-dimeric equilibrium in solution. Addition of phenylacetylene led to the formation of a transient radical species, initiating an alkyne C-H bond activation process. The unusual C-H activation method is applicable for efficient synthesis of propargylamines within 16 hours, demonstrating structural stability and redox retention.