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

• Published in: Angewandte Chemie International Edition Vol. 60; no. 30; pp. 16529 - 16538
• Main Authors: Liu, Zhiqiang, Kole, Goutam Kumar, Budiman, Yudha P., Tian, Ya‐Ming, Friedrich, Alexandra, Luo, Xiaoling, Westcott, Stephen A., Radius, Udo, Marder, Todd B.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 19.07.2021; Wiley Subscription Services, Inc; John Wiley and Sons Inc
• Edition: International ed. in English
• Subjects: 1,2-addition reaction; alcohol; Alcohols; Aldehydes; boronate esters; Carbonyl compounds; Carbonyls; Catalysts; Chemistry; Chemistry, Multidisciplinary; Esters; fluoroarene; Hydrogen bonding; Ketones; Physical Sciences; Science & Technology; transition metal-free; Transition metals; alcohol; SINGLE-CRYSTAL STRUCTURES; ARYLATION; ENANTIOSELECTIVE ADDITION; fluoroarene; ARYLBORONIC ACIDS; 1/1 COMPLEXES; 2-addition reaction; ARENE-PERFLUOROARENE INTERACTIONS; ALKENYLBORONIC ACIDS; 1; ORGANOBORONIC ACIDS; boronate esters; NICKEL; PHASE-BEHAVIOR; transition metal-free; 1,2-addition reaction; boronate ester; fluorine
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202103686

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. 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 %.