Chemoselective Hydrogenation of Imides Catalyzed by Cp*Ru(PN) Complexes and Its Application to the Asymmetric Synthesis of Paroxetine

Ito, Masato; Sakaguchi, Ayaka; Kobayashi, Chika; Ikariya, Takao

doi:10.1021/ja067777y

Cited by 171 publications

(65 citation statements)

References 7 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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“…Since the electronic effect of the chelating amine ligands on both amido and amine complexes might conflict each other, even a slight change in the electronic properties of the amine ligands causes a significant change in the catalytic performance [22,56]. In fact, Cp*Ru(P-N) complex efficiently catalyzes the hydrogenation of imides, while Cp*Ru(N-N) is totally inactive [57]. The electron-withdrawing nature of the P-N ligand might enhance the Lewis acidity of the NH proton in the hydrido complex Cp*RuH[(C 6 H 5 ) 2 P(CH 2 ) 2 NH 2 ], leading to facile activation of polar functionalities imides with the hydride complex.…”

Section: Hydrogenation Of Imidesmentioning

confidence: 99%

“…12 [57]. This hydrogenation method is characterized by its excellent chemoselectivity, substrate scope, and controllable stereoselectivity by the chiral modification of the ligand structures.…”

Section: Hydrogenation Of Imidesmentioning

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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“…The developed reaction system was successfully applied to the enantioselective synthesis of (Ϫ)-paroxetine 103 (Chart 13). [156][157][158][159][160][161][162][163] First, Ir-catalyzed asymmetric allylic alkylation of 104 with dimethyl malonate was performed using (R,S P )-1d, affording 105 in 90% yield (branched/linearϭ99/1) with 92% ee. Hydroboration of the olefin with 9-BBN in the presence of Wilkinson's catalyst, followed by work-up with hydrogen peroxide, gave 106 in 85% yield.…”

Section: )mentioning

confidence: 99%

Transition Metal-Catalyzed Asymmetric Reactions Using P-Chirogenic Diaminophosphine Oxides: DIAPHOXs

Nemoto

2008

CHEMICAL & PHARMACEUTICAL BULLETIN

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This review describes the development of a new class of chiral phosphorus ligands: amino acid-derived Pchirogenic diaminophosphine oxides, DIAPHOXs, and their application to several transition metal-catalyzed asymmetric allylic substitution reactions. Pd-catalyzed asymmetric allylic alkylation with cyclic b b-keto esters as prochiral nucleophiles was initially examined using P-chirogenic diaminophosphine oxide 1a, resulting in highly enantioselective construction of quaternary stereocenters. Mechanistic investigations revealed that 1a is activated by N,O-bis(trimethylsilyl)acetamide-induced tautomerization to afford a trivalent diamidophosphite species 13, which functions as the actual ligand. Pd-catalyzed asymmetric allylic substitutions of both acyclic and cyclic substrates were also examined using various nucleophiles such as malonate derivatives, nitromethane, aliphatic amines, and aromatic amines, providing a variety of chiral compounds with good to excellent enantioselectivity. In addition, Ir-catalyzed asymmetric allylic amination and alkylation of terminal allylic carbonates were examined using structurally optimized P-chirogenic diaminophosphine oxides, and the corresponding branched products were obtained in a highly regio-and enantioselective manner. Furthermore, the developed catalytic asymmetric process was successfully applied to the catalytic enantioselective synthesis of biologically active compounds, (R)-preclamol, (R)-baclofen hydrochloride, and (؊)-paroxetine.

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Chemoselective Hydrogenation of Imides Catalyzed by Cp*Ru(PN) Complexes and Its Application to the Asymmetric Synthesis of Paroxetine

Abstract: ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Cited by 171 publications

References 7 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

Transition Metal-Catalyzed Asymmetric Reactions Using P-Chirogenic Diaminophosphine Oxides: DIAPHOXs

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