Transition Metal Catalyst-Free, Base-Promoted 1,2-Additions of Polyfluorophenylboronates to Aldehydes and Ketones

A novel protocol for the transition metal-free 1,2-addition of polyfluoroaryl boronate esters to aldehydes and ketones is reported, which provides secondary alcohols, tertiary alcohols, and ketones. Control experiments and DFT calculations indicate that both the ortho-F substituents on the polyfluorophenyl boronates and the counterion K+ in the carbonate base are critical. The distinguishing features of this procedure include the employment of commercially available starting materials and the broad scope of the reaction with a wide variety of carbonyl compounds giving moderate to excellent yields. Intriguing structural features involving O-H...O and O-H...N hydrogen bonding, as well as arene-perfluoroarene interactions, in this series of racemic polyfluoroaryl carbinols have also been addressed.

Automated summary

A novel protocol for transition metal-free 1,2-addition of polyfluoroaryl boronate esters to aldehydes and ketones provides various secondary alcohols, tertiary alcohols, and ketones. Control experiments and DFT calculations suggest the importance of ortho-F substituents on the boronates and K+ counterion in the base. This procedure uses commercially available starting materials and has a broad reaction scope, yielding moderate to excellent results with a variety of carbonyl compounds.