Chemoselective oxidation of aryl organoboron systems enabled by boronic acid-selective phase transfer† †Electronic supplementary information (ESI) available: Experimental procedures, assay details and spectra, characterization data for all compounds. See DOI: 10.1039/c6sc04014d Click here for additional data file.

نویسندگان

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

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.

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منابع مشابه

Enantioselective α-amination enabled by a BINAM-derived phase-transfer catalyst† †Electronic supplementary information (ESI) available: Procedures and characterization data. CCDC 1025135. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc02494j Click here for additional data file. Click here for additional data file.

Chiral anion phase-transfer of aryldiazonium cations was utilized to achieve highly enantioselective α-amination of carbonyl compounds. A broad scope of indanone- and benzosuberone-derived substrates was amenable to this strategy. Critical to obtaining high levels of enantioselectivity was the use of BINAM-derived phosphoric acids. The utility of this transformation was demonstrated through fac...

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عنوان ژورنال:

دوره 8  شماره 

صفحات  -

تاریخ انتشار 2017