Iridium-PPh 3 Catalysts for Conversion of Amides to Enamines

Yuta Une, Atsushi Tahara, Yasumitsu Miyamoto, Yusuke Sunada, Hideo Nagashima

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Studies on the deactivation mechanism of the reaction of N,N-dialkylamides with TMDS catalyzed by Vaska's complex, IrCl(CO)(PPh 3 ) 2 (1a), triggered the discovery of highly active Ir-PPh 3 catalysts: Photochemically activated 1a and thermally activated IrCl(PPh 3 ) 3 (8). Both catalysts showed excellent activity toward the selective conversion of a variety of N,N-dialkyl-, N-alkyl-N-aryl-, and N,N-diarylamides to the corresponding enamines with low catalyst loadings. The 14-electron species "ClIr(PPh 3 ) 2 ", which is stabilized by solvents or reactants in the actual catalytic reactions, could be involved in the catalysis, which produces "HIr(PPh 3 ) 2 " and "SiIr(PPh 3 ) 2 " (Si = Me 2 HSiOMe 2 Siâ') species in the catalytic cycle. An in situ generation method for the "ClIrL 2 " species was established by simply mixing [IrCl(Ε 4 -COD)] 2 with PPh 3 or other phosphorus ligands, which realized the facile large-scale syntheses of enamines.

Original languageEnglish
Pages (from-to)852-862
Number of pages11
JournalOrganometallics
Volume38
Issue number4
DOIs
Publication statusPublished - Feb 25 2019

Fingerprint

Iridium
iridium
Amides
amides
catalysts
Catalysts
crack opening displacement
Carbon Monoxide
deactivation
Phosphorus
Catalysis
catalysis
phosphorus
Ligands
ligands
cycles
Electrons
synthesis
electrons

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Iridium-PPh 3 Catalysts for Conversion of Amides to Enamines . / Une, Yuta; Tahara, Atsushi; Miyamoto, Yasumitsu; Sunada, Yusuke; Nagashima, Hideo.

In: Organometallics, Vol. 38, No. 4, 25.02.2019, p. 852-862.

Research output: Contribution to journalArticle

Une, Yuta ; Tahara, Atsushi ; Miyamoto, Yasumitsu ; Sunada, Yusuke ; Nagashima, Hideo. / Iridium-PPh 3 Catalysts for Conversion of Amides to Enamines In: Organometallics. 2019 ; Vol. 38, No. 4. pp. 852-862.
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