Quadruple Role of Pd Catalyst in Domino Reaction Involving Aryl to Alkyl 1,5-Pd Migration to Access 1,9-Bridged Triptycenes

Takayuki Iwata, Satoru Kumagai, Tatsuro Yoshinaga, Masato Hanada, Yoshihito Shiota, Kazunari Yoshizawa, Mitsuru Shindo

Research output: Contribution to journalArticlepeer-review

Abstract

A Pd-catalyzed domino reaction of 1,8,13-tribromo-9-methoxytriptycenes is reported. Under conventional Suzuki coupling conditions, the triptycenes underwent multiple transformations to give 1,9-bridged triptycenes. Based on mechanistic investigations, a single Pd catalyst functions as Pd0, PdII and PdIV species to catalyze four distinct processes: (1) aryl to alkyl 1,5-Pd migration, (2) intramolecular arylation, (3) homocoupling of phenylboronic acid and (4) Suzuki coupling. DFT calculations revealed that 1,5-Pd migration likely proceeds via both concerted PdII and stepwise PdIV routes. Asymmetric synthesis of the chiral triptycenes, as well as optical resolution, and further transformation are also reported.

Original languageEnglish
Pages (from-to)11548-11553
Number of pages6
JournalChemistry - A European Journal
Volume27
Issue number45
DOIs
Publication statusPublished - Aug 11 2021

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

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