Chemoselective oxidation of aryl organoboron systems enabled by boronic acid-selective phase transfer

John J. Molloy, Thomas Aidan Clohessy, Craig Irving, Niall A. Anderson, Guy C. Lloyd-Jones, Allan J. B. Watson

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

We report the direct chemoselective Brown-type oxidation of aryl organoboron systems containing two oxidizable boron groups. Basic biphasic reaction conditions enable selective formation and phase transfer of a boronic acid trihydroxyboronate in the presence of boronic acid pinacol (BPin) esters, while avoiding speciation equilibria. Spectroscopic investigations validate a base-promoted phase-selective discrimination of organoboron species. This phenomenon is general across a broad range of organoboron compounds and can also be used to invert conventional protecting group strategies, enabling chemoselective oxidation of BMIDA species over normally more reactive BPin substrates. We also demonstrate the selective oxidation of diboronic acid systems with chemoselectivity predictable a priori. The utility of this method is exemplified through the development of a chemoselective oxidative nucleophile coupling.
LanguageEnglish
JournalChemical Science
Early online date27 Oct 2016
DOIs
Publication statusE-pub ahead of print - 27 Oct 2016

Fingerprint

Boronic Acids
Oxidation
Nucleophiles
Boron
Esters
Acids
Substrates

Keywords

  • aryl organoboron
  • organoboron compounds
  • chemoselective oxidative nucleophile coupling

Cite this

Molloy, John J. ; Clohessy, Thomas Aidan ; Irving, Craig ; Anderson, Niall A. ; Lloyd-Jones, Guy C. ; Watson, Allan J. B. / Chemoselective oxidation of aryl organoboron systems enabled by boronic acid-selective phase transfer. In: Chemical Science. 2016.
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Chemoselective oxidation of aryl organoboron systems enabled by boronic acid-selective phase transfer. / Molloy, John J.; Clohessy, Thomas Aidan; Irving, Craig; Anderson, Niall A.; Lloyd-Jones, Guy C.; Watson, Allan J. B.

In: Chemical Science, 27.10.2016.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Chemoselective oxidation of aryl organoboron systems enabled by boronic acid-selective phase transfer

AU - Molloy, John J.

AU - Clohessy, Thomas Aidan

AU - Irving, Craig

AU - Anderson, Niall A.

AU - Lloyd-Jones, Guy C.

AU - Watson, Allan J. B.

PY - 2016/10/27

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N2 - We report the direct chemoselective Brown-type oxidation of aryl organoboron systems containing two oxidizable boron groups. Basic biphasic reaction conditions enable selective formation and phase transfer of a boronic acid trihydroxyboronate in the presence of boronic acid pinacol (BPin) esters, while avoiding speciation equilibria. Spectroscopic investigations validate a base-promoted phase-selective discrimination of organoboron species. This phenomenon is general across a broad range of organoboron compounds and can also be used to invert conventional protecting group strategies, enabling chemoselective oxidation of BMIDA species over normally more reactive BPin substrates. We also demonstrate the selective oxidation of diboronic acid systems with chemoselectivity predictable a priori. The utility of this method is exemplified through the development of a chemoselective oxidative nucleophile coupling.

AB - We report the direct chemoselective Brown-type oxidation of aryl organoboron systems containing two oxidizable boron groups. Basic biphasic reaction conditions enable selective formation and phase transfer of a boronic acid trihydroxyboronate in the presence of boronic acid pinacol (BPin) esters, while avoiding speciation equilibria. Spectroscopic investigations validate a base-promoted phase-selective discrimination of organoboron species. This phenomenon is general across a broad range of organoboron compounds and can also be used to invert conventional protecting group strategies, enabling chemoselective oxidation of BMIDA species over normally more reactive BPin substrates. We also demonstrate the selective oxidation of diboronic acid systems with chemoselectivity predictable a priori. The utility of this method is exemplified through the development of a chemoselective oxidative nucleophile coupling.

KW - aryl organoboron

KW - organoboron compounds

KW - chemoselective oxidative nucleophile coupling

U2 - 10.1039/C6SC04014D

DO - 10.1039/C6SC04014D

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