Transition Metal Catalyst‐Free, Base‐Promoted 1, 2‐Additions of Polyfluorophenylboronates to Aldehydes and Ketones. Issue 30 (17th June 2021)

• Record Type: Journal Article
• Authors: Liu, Zhiqiang; Kole, Goutam Kumar; Budiman, Yudha P.; Tian, Ya‐Ming; Friedrich, Alexandra; Luo, Xiaoling; Westcott, Stephen A.; Radius, Udo; Marder, Todd B.
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 30(2021)
• Page Start: 16529
• Page End: 16538
• Publication Date: 2021-06-17
• Subjects: alcohol -- 1, 2-addition reaction -- boronate esters -- fluoroarene -- transition metal-free; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202103686
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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. Abstract : Herein we report a transition metal‐free procedure for the base‐promoted 1, 2‐addition of polyfluorophenylboronates to aldehydes and ketones to generate organofluorine‐containing alcohols in yields up to 93 %.