A Pd-catalyzed organometallic-free homologation of arylboronic acids enabled by chemoselective transmetalation

Kane A. C. Bastick, Allan J. B. Watson*

*Corresponding author for this work

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Abstract

A Pd-catalyzed homologation of arylboronic acids is reported. Halomethylboronic acid pinacol esters (Bpin) undergo a remarkably facile, yet rare, oxidative addition enabled by an α-boryl effect. Simultaneous chemoselective transmetalation allows use of these metalloid reagents for formal C1 insertion to deliver benzyl Bpin products without the requirement for stoichiometric organometallic reagents. The utility of the process is demonstrated by stepwise C(sp3)–C(sp2) cross-coupling of the boronic ester products into diarylmethane pharmacophores and electrophile/nucleophile chemoselective cross-coupling. Control experiments that demonstrate the reactivity enhancement provided by the α-boryl effect are provided, along with a description of the limitations of the formal homologation process.
Original languageEnglish
Pages (from-to)7013–7018
Number of pages6
JournalACS Catalysis
Volume13
Issue number10
Early online date9 May 2023
DOIs
Publication statusPublished - 19 May 2023

Keywords

  • Boron
  • Catalysis
  • Chemoselectivity
  • Cross-coupling
  • Homologation
  • Palladium

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