Iridium-PPh 3 Catalysts for Conversion of Amides to Enamines

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

研究成果: ジャーナルへの寄稿記事

2 引用 (Scopus)

抄録

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.

元の言語英語
ページ(範囲)852-862
ページ数11
ジャーナルOrganometallics
38
発行部数4
DOI
出版物ステータス出版済み - 2 25 2019

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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

これを引用

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

:: Organometallics, 巻 38, 番号 4, 25.02.2019, p. 852-862.

研究成果: ジャーナルへの寄稿記事

Une, Yuta ; Tahara, Atsushi ; Miyamoto, Yasumitsu ; Sunada, Yusuke ; Nagashima, Hideo. / Iridium-PPh 3 Catalysts for Conversion of Amides to Enamines :: Organometallics. 2019 ; 巻 38, 番号 4. pp. 852-862.
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title = "Iridium-PPh 3 Catalysts for Conversion of Amides to Enamines",
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 Si{\^a}') species in the catalytic cycle. An in situ generation method for the {"}ClIrL 2 {"} species was established by simply mixing [IrCl({\^I}• 4 -COD)] 2 with PPh 3 or other phosphorus ligands, which realized the facile large-scale syntheses of enamines.",
author = "Yuta Une and Atsushi Tahara and Yasumitsu Miyamoto and Yusuke Sunada and Hideo Nagashima",
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AU - Nagashima, Hideo

PY - 2019/2/25

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AB - 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.

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