Mechanism and Scope of Nickel-Catalyzed Decarbonylative Borylation of Carboxylic Acid Fluorides

Christian A. Malapit, James R. Bour, Simon R. Laursen, Melanie S. Sanford*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

63 Scopus citations

Abstract

This Article describes the development of a base-free, nickel-catalyzed decarbonylative coupling of carboxylic acid fluorides with diboron reagents to selectively afford aryl boronate ester products. Detailed studies were conducted to assess the relative rates of direct transmetalation between aryl boronate esters and diboron reagents and a bisphosphine nickel(aryl)(fluoride) intermediate. These investigations revealed that diboron reagents undergo transmetalation with this Ni(aryl)(fluoride) intermediate at rates significantly faster than their aryl boronate ester congeners. Furthermore, the reactivity of both boron reagents toward transmetalation is enhanced with increasing electrophilicity of the boron center. These mechanistic insights were leveraged to develop a catalytic decarbonylative borylation of acid fluorides that proved applicable to a variety of (hetero)aryl carboxylic acid fluorides as well as diverse diboron reagents. The acid fluorides can be generated in situ directly from carboxylic acids. Furthermore, the mechanistic studies directed the identification of various air-stable Ni pre-catalysts for this transformation.

Original languageEnglish (US)
Pages (from-to)17322-17330
Number of pages9
JournalJournal of the American Chemical Society
Volume141
Issue number43
DOIs
StatePublished - Oct 30 2019
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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