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Updated: Jun 6, 2025

Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts
Published on: February 24, 2015
Base-Free Borylation of Aryl Halides Enabled by Zn-Promoted Halide Abstraction
Brittany L Gay1, Lauren A Prendeville1, Ya-Nong Wang1
1Department of Chemistry, The University of Texas at Austin, 100 East 24th Street, Austin, Texas 78712, United States.
Abstract:
Herein, we report the palladium-catalyzed borylation of aryl halides (iodides or bromides) under base-free conditions utilizing a commercially available Lewis acidic mediator, Zn(OTf)2. Under these conditions, an array of electronically and functional-group-diverse aryl iodides and bromides undergo borylation to afford the corresponding aryl boronic esters in ≤82% isolated yields. Mechanistic investigations are consistent with Zn(OTf)2 enabling transmetalation between a cationic Pd(II)-Ar intermediate and B2pin2 via halide abstraction. Furthermore, stabilization of the cationic [ArPdII]+ complex with added [BArF4]- significantly improves the reaction efficiency with electron-poor arenes.
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