The AZARYPHOS family of ligands for ambifunctional catalysis

Syntheses and use in ruthenium-catalyzed anti-markovnikov hydration of terminal alkynes

Lukas Hintermann, Tuan Thanh Dang, Aurélie Labonne, Thomas Kribber, Li Xiao, Pance Naumov

Research output: Contribution to journalArticle

Abstract

The family of AZARYPHOS (aza-aryl-phosphane) phosphane ligands, containing a phosphine unit and sterically shielded nitrogen lone pairs in the ligand periphery, is introduced as a tool for developing ambifunctional catalysis by the metal center and nitrogen lone pairs in the ligand sphere. General synthetic strategies have been developed to synthesize over 25 examples of structurally diverse (6-aryl-2pyridyl)phosphanes (ARPYPHOS), (6alkyl-2-pyridyl)phosphanes (ALPY-PHOS), 4,6-disubsituted l,3-diazin-2ylphosphanes or l,3,5-triazin-2- ylphosphanes, quinazolinylphosphanes, quinolinylphosphanes, and others. The scalable syntheses proceed in a few steps. The incorporation of AZARYPHOS ligands (L) into complexes [RuCp(L)2(MeCN)][PF6] (Cp = cyclopentadieny1)gives catalysts for the anti-Markovnikov hydration of terminal alkynes of the highest known activities. Electronic and steric ligand effects modulate the reaction kinetics over a range of two orders of magnitude. These results highlight the importance of using structurally diverse ligand families in the process of developing cooperative ambifunctional catalysis by a metal and its ligand.

Original languageEnglish (US)
Pages (from-to)7167-7179
Number of pages13
JournalChemistry - A European Journal
Volume15
Issue number29
DOIs
StatePublished - Jul 20 2009

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phosphine
Alkynes
Ruthenium
Hydration
Catalysis
Ligands
Nitrogen
Metals
Reaction kinetics

Keywords

  • Alkynes
  • Catalysis
  • Phosphane ligands
  • Ruthenium
  • Synthetic methods

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

The AZARYPHOS family of ligands for ambifunctional catalysis : Syntheses and use in ruthenium-catalyzed anti-markovnikov hydration of terminal alkynes. / Hintermann, Lukas; Dang, Tuan Thanh; Labonne, Aurélie; Kribber, Thomas; Xiao, Li; Naumov, Pance.

In: Chemistry - A European Journal, Vol. 15, No. 29, 20.07.2009, p. 7167-7179.

Research output: Contribution to journalArticle

Hintermann, Lukas ; Dang, Tuan Thanh ; Labonne, Aurélie ; Kribber, Thomas ; Xiao, Li ; Naumov, Pance. / The AZARYPHOS family of ligands for ambifunctional catalysis : Syntheses and use in ruthenium-catalyzed anti-markovnikov hydration of terminal alkynes. In: Chemistry - A European Journal. 2009 ; Vol. 15, No. 29. pp. 7167-7179.
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