One-Pot Miyaura Borylation/Suzuki-Miyuara Cross-Coupling Enabled by the Ester Effect

Bock, Matthew; Chen, Zijian; Sura, Jakub; Lubbs, Jack; Kassel, Vincent

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https://hdl.handle.net/2142/133278 Copy

Description

Title

One-Pot Miyaura Borylation/Suzuki-Miyuara Cross-Coupling Enabled by the Ester Effect

Author(s)

• Bock, Matthew
• Chen, Zijian
• Sura, Jakub
• Lubbs, Jack
• Kassel, Vincent

Issue Date

2026-05-15

Director of Research (if dissertation) or Advisor (if thesis)

Denmark, Scott

Department of Study

Chemistry

Degree Name

B.S. (bachelor's)

Degree Level

Thesis

Date of Ingest

2026-05-15T15:26:30-05:00

Keyword(s)

Suzuki-Miyaura Cross-Coupling, One-Pot, Ester Effect

Language

eng

Abstract

Among methods to prepare biaryl linkages, the Suzuki-Miyaura cross-coupling reaction is one of the most ubiquitous options. Recently, the Denmark group reported an anhydrous, homogenous Suzuki-Miyaura cross-coupling of aryl bromides with neopentyldiol arylboronic esters (BNeop) and potassium trimethylsilanolate (TMSOK), a soluble base. The cross-coupling proceeds rapidly due to the ester effect, a rate increase afforded by boronic esters under anhydrous conditions. Despite these benefits, arylBNeop esters are either expensive or commercially unavailable when compared to other organoboron reagents, rendering this method less accessible to chemical practitioners. Herein, a method for a rapid, one-pot Miyaura borylation/Suzuki-Miyaura cross-coupling of aryl and vinyl halides with B2Neop2 is described. For the borylation step, a combination of cataCXium A third-generation Buchwald precatalyst and potassium 2-ethylhexanoate enabled rapid borylation for aryl, vinyl and heteroaryl halides while mitigating off-cycle reactivity. Subjecting this reaction mixture to the TMSOK-promoted Suzuki-Miyaura cross-coupling with (hetero)aryl bromides enabled successful aryl-aryl bond formation with high yields in 30 min or less, which includes a variety of challenging heteroaryl-heteroaryl products with both π-deficient and π-rich scaffolds. Finally, to further demonstrate the benefit of these anhydrous conditions, proof-of-concept for the elusive one-pot cross-coupling of protodeboronation-prone 2-borylpyridine was established.

Type of Resource

text

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