Base-Free Borylation of Aryl Halides Enabled by Zn-Promoted Halide Abstraction
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)<sub>2</sub>. 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)<sub>2</sub> enabling transmetalation between a cationic Pd(II)-Ar intermediate and B<sub>2</sub>pin<sub>2</sub> via halide abstraction. Furthermore, stabilization of the cationic [ArPd<sup>II</sup>]<sup>+</sup> complex with added [BAr<sup>F</sup><sub>4</sub>]<sup>-</sup> significantly improves the reaction efficiency with electron-poor arenes.
Authors
- Ya‐Nong Wang (ORCID: https://orcid.org/0000-0002-5838-3855)
- Kami L. Hull (ORCID: https://orcid.org/0000-0003-3102-2686)
- Brittany L. Gay (ORCID: https://orcid.org/0000-0002-6481-6071)
- Lauren A. Prendeville
Institutions
- The University of Texas at Austin (US)
Publication Details
- Journal
- Organic Letters
- Published
- 2024-12-03
- DOI
- https://doi.org/10.1021/acs.orglett.4c03821
- Citations
- 7
- Primary Topic
- Catalytic Cross-Coupling Reactions
- Type
- article
- Field-Weighted Citation Impact
- 1.75
Funders
- Eli Lilly and Company
- Novartis
- Division of Chemistry