Base‐Free Pd‐Catalyzed C−Cl Borylation of Fluorinated Aryl Chlorides. Issue 11 (18th January 2021)

• Record Type: Journal Article
• Authors: Budiman, Yudha P.; Lorenzen, Sabine; Liu, Zhiqiang; Radius, Udo; Marder, Todd B.
• Is Part Of: Chemistry. Volume 27:Issue 11(2021)
• Page Start: 3869
• Page End: 3874
• Publication Date: 2021-01-18
• Subjects: boronate ester -- borylation -- cross-coupling -- fluoroarene -- palladium-catalyzed; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202004648
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Catalytic C−X borylation of aryl halides containing two ortho ‐fluorines has been found to be challenging, as most previous methods require stoichiometric amounts of base and the polyfluorinated aryl boronates suffer from protodeboronation, which is accelerated by ortho ‐fluorine substituents. Herein, we report that a combination of Pd(dba)2 (dba=dibenzylideneacetone) with SPhos (2‐dicyclohexylphosphino‐2', 6'‐dimethoxybiphenyl) as a ligand is efficient to catalyze the C‐Cl borylation of aryl chlorides containing two ortho ‐fluorine substituents. This method, conducted under base‐free conditions, is compatible with the resulting di ‐ortho ‐fluorinated aryl boronate products which are sensitive to base. Abstract : The best base is no base ! We report an efficient method for the palladium‐catalyzed C−Cl borylation of aryl chlorides containing two ortho ‐fluorines. The reactions are conducted under base‐free conditions to avoid decomposition of the products which are sensitive to base.