Highly Efficient Chemoselective Hydrogenolysis of Epoxides Catalyzed by a (η5-C5(CH3)5)Ru Complex Bearing a 2-(Diphenylphosphino)ethylamine Ligand

Ito, Masato; Hirakawa, Makoto; Osaku, and Akihide; Ikariya, Takao

doi:10.1021/om034006j

Cited by 95 publications

(79 citation statements)

References 19 publications

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“…17 Crucially, the chelating amine ligand makes the catalyst more resistant to undesirable M-N bond cleavage. 18 Other chelating groups such as aryl, 19 phosphine [20][21][22] and thiol/thioether 23 have also been used to tether the reactive nitrogen to the metal in transfer hydrogenation. However, the application of N-heterocyclic carbene (NHC) donor groups to tether a nucleophilic amido ligand to an electrophilic metal in bifunctional catalysis has yet to be fully exploited, 24,25 and even simple coordination chemistry of multidentate amido-NHC ligands is under-explored.…”

Section: Introductionmentioning

confidence: 99%

N-heterocyclic carbene tethered amido complexes of palladium and platinum

et al. 2011

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Graphical Contents EntryThe synthesis and structure of chelating amido-NHC and amido-bis(NHC) complexes of Pd and Pt are described, including the first [CNC]Pt complexes and the first Pd arylamido-NHC complex. AbstractWith a view to applications in bifunctional catalysis, a modular cross-coupling strategy has been used to prepare amine bis(imidazolium) salts (3a and 3b) and an amine mono(imidazolium) salt (6) inert Pt analogue 11 was unreactive under the same conditions. Solid-state structures of the complexes 7a, 7b, 9a, 10, 11 and 12 have been determined by single crystal X-ray diffraction.

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Section: Introductionmentioning

confidence: 99%

N-heterocyclic carbene tethered amido complexes of palladium and platinum

et al. 2011

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“…Alkenyl epoxides gave secondary alkenyl alcohols in quantitative yield without formation of saturated alcohols or epoxides. Terminal epoxides bearing another oxygen functionality on the side chain also undergo hydrogenolysis to afford the corresponding secondary alcohols in good yields, indicating that groups next to the epoxide group do not interact with the metal center because of the Ru/NH bifunctionality of the Cp*Ru catalyst [64]. Although stereospecific hydrogenolysis of chiral terminal epoxides was hampered by the competing racemization of the chiral product alcohols (vide infra), this catalytic hydrogenolysis provides a new alternative to stoichiometric metal hydride reduction.…”

Section: Hydrogenolysis Of Epoxidesmentioning

confidence: 99%

“…In fact, asymmetric hydrogenation of prochiral ketones becomes possible with chiral Cp*Ru(N-N) catalyst system, thanks to its reluctance to dehydrogenate alcohols, but not with chiral Cp*Ru(P-N) systems since concurrent racemization of the product alcohols deteriorates the ee value of the alcoholic products regardless of whether the hydrogen source is H 2 or 2-propanol [64,65]. Two synthetically viable, oxidative transformations of alcohols have been successfully developed.…”

Section: Dehydrogenative Oxidation Of Alcohols With Cp*ru(p-n) Catalystsmentioning

confidence: 99%

Bifunctional Transition Metal-Based Molecular Catalysts for Asymmetric Syntheses

Ikariya

2011

Bifunctional Molecular Catalysis

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The discovery and development of conceptually new chiral bifunctional molecular catalysts based on the metal/NH acid-base synergy effect are described. The chiral bifunctional molecular catalysis originally developed for asymmetric transfer hydrogenation of ketones is applicable in enantioselective hydrogenation of polar functionalities as well as practical oxidative reactions including aerobic oxidation of alcohols. The structural modification and electronic fine-tuning of the protic amine chelating ligands are crucial to develop unprecedented catalytic reactions. The present bifunctional transition metal-based molecular catalyst offers a great opportunity to open up new fundamentals for stereoselective molecular transformations.

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“…29 The [Cp*Ru(PN)] catalyst can also discriminate the polarized CO bonds in the epoxides from less polarized C=C bonds to allow chemoselective hydrogenation leading to alkenyl alcohols. Although stereospecific hydrogenolysis of optically active terminal epoxides was hampered by the competing racemization of the product alcohols, this catalytic hydrogenolysis provides a new alternative to stoichiometric metal hydride reduction.…”

Section: Asymmetric Transfer Hydrogenation Of C=o and C=n Double Bondmentioning

confidence: 99%

Chemistry of Concerto Molecular Catalysis Based on the Metal/NH Bifunctionality

Ikariya¹

2010

Bulletin of the Chemical Society of Japan

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124

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The development of conceptually new bifunctional transition-metal-based catalysts for a wide range of catalytic reactions is described. The bifunctional chiral molecular catalyst based on metalligand cooperation was originally developed for asymmetric transfer hydrogenation of ketones and imines and is now applicable to chemo-and stereoselective reductive and oxidative transformations as well as to enantioselective CC and CN bond formations with a wide scope and high practicability. The structural modification and electronic fine-tuning of the protic amine chelating ligands are crucial to develop unprecedented catalytic reactions. Cp*Ru complexes bearing a diamine (NN) or aminophosphine (PN) ligand readily activate H 2 , and can effect hydrogenation of polar functionalities. The bifunctional Ir complexes promote aerobic oxidative transformation of alcohols into ketones and esters and are applicable to kinetic resolution of racemic secondary alcohols. A novel imido-bridged dirhodium complex, which is a dinuclear variant of the bifunctional mononuclear amido complexes, promotes aerobic oxidation of a secondary alcohol and H 2 . In addition, the metal/NH bifunctional property also affects efficiently enantioselective conjugate additions. The present concerto molecular catalysts offer a great opportunity to open up new fundamentals for stereoselective molecular transformations.

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Highly Efficient Chemoselective Hydrogenolysis of Epoxides Catalyzed by a (η⁵-C₅(CH₃)₅)Ru Complex Bearing a 2-(Diphenylphosphino)ethylamine Ligand

Abstract: Terminal epoxides are hydrogenolyzed to give secondary alcohols with high regioselectivity using the ternary catalyst system of CpRuCl(cod)−2-(diphenylphosphino)ethylamine (1a)−KOH (Cp = η5-C5(CH3)5, cod = 1,5-cyclooctadiene) in 2-propanol under mild conditions.

Cited by 95 publications

References 19 publications

N-heterocyclic carbene tethered amido complexes of palladium and platinum

N-heterocyclic carbene tethered amido complexes of palladium and platinum

Bifunctional Transition Metal-Based Molecular Catalysts for Asymmetric Syntheses

Chemistry of Concerto Molecular Catalysis Based on the Metal/NH Bifunctionality

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Highly Efficient Chemoselective Hydrogenolysis of Epoxides Catalyzed by a (η5-C5(CH3)5)Ru Complex Bearing a 2-(Diphenylphosphino)ethylamine Ligand

Abstract: Terminal epoxides are hydrogenolyzed to give secondary alcohols with high regioselectivity using the ternary catalyst system of Cp*RuCl(cod)−2-(diphenylphosphino)ethylamine (1a)−KOH (Cp* = η5-C5(CH3)5, cod = 1,5-cyclooctadiene) in 2-propanol under mild conditions.

Cited by 95 publications

References 19 publications

N-heterocyclic carbene tethered amido complexes of palladium and platinum

N-heterocyclic carbene tethered amido complexes of palladium and platinum

Bifunctional Transition Metal-Based Molecular Catalysts for Asymmetric Syntheses

Chemistry of Concerto Molecular Catalysis Based on the Metal/NH Bifunctionality

Contact Info

Product

Resources

About

Highly Efficient Chemoselective Hydrogenolysis of Epoxides Catalyzed by a (η⁵-C₅(CH₃)₅)Ru Complex Bearing a 2-(Diphenylphosphino)ethylamine Ligand

Abstract: Terminal epoxides are hydrogenolyzed to give secondary alcohols with high regioselectivity using the ternary catalyst system of CpRuCl(cod)−2-(diphenylphosphino)ethylamine (1a)−KOH (Cp = η5-C5(CH3)5, cod = 1,5-cyclooctadiene) in 2-propanol under mild conditions.