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Transition Metal Catalyst‐Free, Base‐Promoted 1,2‐Additions of Polyfluorophenylboronates to Aldehydes and Ketones
Author(s) -
Liu Zhiqiang,
Kole Goutam Kumar,
Budiman Yudha P.,
Tian YaMing,
Friedrich Alexandra,
Luo Xiaoling,
Westcott Stephen A.,
Radius Udo,
Marder Todd B.
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202103686
Subject(s) - chemistry , transition metal , catalysis , counterion , dimethyl carbonate , base (topology) , ketone , organic chemistry , base metal , carbonate , primary (astronomy) , metal , combinatorial chemistry , materials science , ion , mathematical analysis , mathematics , welding , metallurgy , physics , astronomy
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.