Piers' Borane-Catalyzed Dimerization of Arylallenes via Transborylation: A Synthetic and Mechanistic Study

Ravindra S. Phatake, Arthur Averdunk, Christian Würtele, Urs Gellrich

Research output: Contribution to journalArticlepeer-review

Abstract

Herein, we report a Piers' borane-catalyzed dimerization of arylallenes. Catalytic turnover is achieved by a transborylation with pinacolborane (HBpin) that releases Piers' borane and promotes the catalytic reaction, thereby giving convenient access to a range of synthetically versatile bench-stable pinacolborane-substituted 1,5-dienes. The synthetic utility of these pinacolborane-substituted 1,5-dienes was demonstrated by Suzuki-Miyaura coupling, the synthesis of azide and halogen-substituted 1,5-dienes, and the oxidation to γ,unsaturated aryl ketones. The mechanism of the reaction was investigated experimentally as well as by dispersion-corrected double-hybrid density functional theory (DFT) computations. These investigations indicate that Piers' borane mediates the allene dimerization and a subsequent Cope rearrangement to yield a B(C6F5)2-substituted 1,5-diene. This diene then undergoes a transborylation via a concerted σ-bond metathesis at the final stage of the catalytic reaction.

Original languageEnglish
Pages (from-to)13961-13968
Number of pages8
JournalACS Catalysis
DOIs
StateAccepted/In press - 1 Jan 2022
Externally publishedYes

Keywords

  • DFT computation
  • diene
  • Lewis acid
  • main-group catalysis
  • transborylation

ASJC Scopus subject areas

  • Catalysis
  • Chemistry (all)

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