Empirical and Computational Insights into N-Arylation Reactions Catalyzed by Palladium meta-Terarylphosphine Catalyst

Fui Fong Yong, Adrian M. Mak, Wenqin Wu, Michael B. Sullivan, Edward G. Robins, Charles W. Johannes, Howard Jong, Yee Hwee Lim

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)

Abstract

An in situ generated Pd–Cy*Phine catalyst has been successfully applied to the N-arylation of primary and secondary amines, and it exhibited high performance across multiple substrate classes. The performance induced by the meta-terarylphosphine motif of the Cy*Phine ligand for C−N cross-coupling displayed only subtle differences to that of its biarylphosphine congener XPhos. DFT studies demonstrated comparable reaction energetics in the catalytic cycle steps for both Pd–Cy*Phine and Pd–XPhos, which was consistent with previous findings. The computational investigation also indicated that a putative rate-determining step occurred after amine binding, which was likely to have annulled the expected benefits of having a meta-terarylphosphine ligand architecture.

Original languageEnglish
Pages (from-to)750-757
Number of pages8
JournalChemPlusChem
Volume82
Issue number5
DOIs
Publication statusPublished or Issued - 1 May 2017
Externally publishedYes

Keywords

  • amines
  • arylation
  • cross-coupling
  • homogeneous catalysis
  • palladium

ASJC Scopus subject areas

  • Chemistry(all)

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