A Pivotal Role of Chloride Ion on Nickel-Catalyzed Enantioselective Reductive Cross-Coupling to Perfluoroalkylated Boronate Esters

The enantioselective construction of perfluoroalkyl-containing molecules is essential in materials science, agrochernistry, and medicinal chemistry. Herein, a nickel-catalyzed reductive cross-coupling was reported to generate chiral perfluoroalkylated boronate esters from the easily ATRA prepared perfluoroalkyl-substituted alpha-iodoboronates. The simple and mild conditions enable a broad range of aryl iodides to deliver the products in good enantioselectivities. Additionally, compared with common acceleration by iodide salts on substrate activation, the effect of the additive was systematically investigated to disclose a pivotal role of chloride ion on nickel reduction for this transformation.

Automated summary

In this study, chiral perfluoroalkylated boronate esters were successfully synthesized using a nickel-catalyzed method, under simple and mild conditions suitable for a wide range of aryl iodides. The role of chloride ion in nickel reduction for this transformation was systematically investigated, revealing its pivotal function.