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Organoboron compounds are well known building blocks for many organic reactions. However, under basic conditions, polyfluorinated aryl boronic acid derivatives suffer from instability issues that are accelerated in compounds containing an ortho‐fluorine group, which result in the formation of the corresponding protodeboronation products. Therefore, a considerable amount of research has focused on novel methodologies to synthesize these valuable compounds while avoiding the protodeboronation issue. This review summarizes the latest developments in the synthesis of fluorinated aryl boronic acid derivatives and their applications in cross‐coupling reactions and other transformations.
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We report herein a mild procedure for the copper‐catalyzed oxidative cross‐coupling of electron‐deficient polyfluorophenylboronate esters with terminal alkynes. This method displays good functional group tolerance and broad substrate scope, generating cross‐coupled alkynyl(fluoro)arene products in moderate to excellent yields. Thus, it represents a simple alternative to the conventional Sonogashira reaction.
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.