Iridium-PPh 3 Catalysts for Conversion of Amides to Enamines

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

Research output: Contribution to journalArticlepeer-review

6 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

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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