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

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...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 141; no. 43; pp. 17322 - 17330
Main Authors Malapit, Christian A, Bour, James R, Laursen, Simon R, Sanford, Melanie S
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 30.10.2019
Amer Chemical Soc
Subjects
Air
Boron Compounds - chemistry
Carboxylic Acids - chemistry
Catalysis
Chemistry
Chemistry, Multidisciplinary
Esters - chemistry
Fluorides - chemistry
Indicators and Reagents - chemistry
Magnetic Resonance Spectroscopy
Molecular Structure
Nickel - chemistry
Physical Sciences
Science & Technology
HALIDES
LEWIS-BASE ADDUCTS
ACTIVATION
DESIGN
CROSS-COUPLING REACTION
TRANSMETALATION
STRATEGY
ESTERS
ARYL CHLORIDES
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Summary: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.
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ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.9b08961