Asymmetric Hydrogenation of Ketones Using a Ruthenium(II) Catalyst Containing BINOL-Derived Monodonor Phosphorus-Donor Ligands

Xu, Ye; Alcock, N. W.; Clarkson, Guy J.; Docherty, Gordon; Woodward, Gary; Wills, Martin

doi:10.1021/ol0481840

Cited by 69 publications

(45 citation statements)

References 34 publications

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“…Again, the configuration of the product changed with the configuration of the diamine used. Use of ligand 1c containing 6,6'-dibromo substituents on the BINOL gave similar results as with ligand 1a (entries 11,12). Use of the octahydro-BINOL-based ligand 2 led to 60% ee in the case of the matched ligands; the mismatched combination led to only 39% ee (entries 13,14).…”

Section: Resultsmentioning

confidence: 67%

“…This alcohol is an intermediate for the antiemetic Aprepitant TM (entry 10). [23] Both 1-and 2-acetonaphthones were hydrogenated with excellent ee (entries 11,12). Although propiophenone (entry 13) and butyrophenone (entry 14) were hydrogenated with very high enantioselectivity, surprisingly, 2-methylpropiophenone was a sluggish substrate (entry 15).…”

Section: Resultsmentioning

confidence: 99%

“…[10] Better results were obtained by Wills and co-workers who tested a range of BINOL-based monodentate ligands in ruthenium-catalysed aromatic ketone hydrogenation. [11] Full conversion and exellent ees (up to 99%) were reached in the hydrogenation of acetophenones, using the monodentate phosphonite ligand BrXuPhos (Figure 1) in combination with 1,2-diphenylethylene-1,2-diamine (DPEN) (denoted as NN in Figure 1).…”

Section: Introductionmentioning

confidence: 99%

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Ruthenium‐Catalysed Hydrogenation of Aromatic Ketones using Monodentate Phosphoramidite Ligands

et al. 2010

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A ruthenium pre-catalyst containing two equivalents of the bulky monodentate phosphoramidite 3,3'-dimethyl-PipPhos and one equivalent of a chiral diamine such as 1,2-diphenylethylenediamine or 1,2-diaminocyclohexane was used for the asymmetric hydrogenation of aromatic ketones. A range of substituted and unsubstituted aryl alkyl ketones was hydrogenated using only 0.1 mol% of this catalyst with full conversions and enantioselectivities up to 97%. The phosphoramidite and diamine ligands matched when both had the same configuration, i.e., S-phosphoramidite with S,S-diamine. In that case the product was obtained with high enantioselectivity and the R-configuration. The mismatched case produced the product in lower ee. The product configuration was determined by the configuration of the diamine ligand. A mechanistic proposal was made.

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Section: Resultsmentioning

confidence: 67%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ruthenium‐Catalysed Hydrogenation of Aromatic Ketones using Monodentate Phosphoramidite Ligands

et al. 2010

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“…It was Noyori's catalyst trans-[RuCl2(diphosphane) (1,2-diamine)] that first enabled the enantioselective hydrogenation of C=O double bond of , -unsaturated ketones and cyclic enones. [15] Unfuctionalized ketones, and more specifically aromatic ketones, were investigated by Xu et al [36] The research group discovered that a Ru(II) catalyst containing the BINOL backbone ( Figure 5a) is able to successfully hydrogenate a wide range of aromatic ketones, with high yields and up to 99% e.e. All reactions are conducted in 2-propanol.…”

Section: The Case Of Ketonesmentioning

confidence: 99%

Homogeneous Chemoselective Hydrogenation of Heterocyclic Compounds – The Case of 1,4 Addition on Conjugated C-C and C-O Double Bonds of Arylidene Tetramic Acids

Karaiskos¹,

Matiadis²,

Markopoulos³

et al. 2012

Hydrogenation

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“…[13][14][15][16] No Ru/diphosphinite/diamine complexes have been investigated for the transfer hydrogenation of prochiral ketones although such complexes with monodentate phosphinite ligands have been used recently for such H 2 -hydrogenations. 17 Our group previously reported that ruthenium phosphine diamine hydrido complexes are effective precatalysts for the H 2 -hydrogenation and transfer hydrogenation of prochiral ketones and imines to give optically active alcohols and amines. 18 Herein, we report the convenient, modular synthesis and characterization of complexes of the type transRuHCl(diphosphinite)(diamine) and their application in the asymmetric transfer hydrogenation of ketones.…”

mentioning

confidence: 99%

A modular design of ruthenium catalysts with diamine and BINOL-derived phosphinite ligands that are enantiomerically-matched for the effective asymmetric transfer hydrogenation of simple ketones

et al. 2005

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A method is reported for making a potentially very wide series of ruthenium hydrido chloro complexes with diamine and readily-prepared diphosphinite ligand modules as precatalysts for the asymmetric transfer hydrogenation of simple ketones to give chiral alcohols in good yield and enantioselectivity.Chiral alcohols are very important building blocks and synthetic intermediates in organic synthesis and the pharmaceutical industry.1,2 The reduction of prochiral ketones to give chiral alcohols is among the most fundamental subjects in modern synthetic chemistry. Noyori and co-workers provided an elegant solution for the asymmetric catalytic H 2 -hydrogenation of simple aryl ketones. Herein, we report the convenient, modular synthesis and characterization of complexes of the type transRuHCl(diphosphinite)(diamine) and their application in the asymmetric transfer hydrogenation of ketones. This approach allows the opportunity for rapid tuning of the catalyst structure due to the modular nature of the ligands and precatalysts.A wide variety of catalyst structures are readily constructed from three modules A-C. First BINOL (A, (R) or (S)) and diarylchlorophosphine (B, Ar 5 Ph or 3,5-Me 2 C 6 H 3 (xyl)) are combined to give the phosphinite ligand. Then this is reacted with RuHCl(PPh 3 ) 3 to produce an intermediate complex RuHCl(diphosphinite)(PPh 3 ) that is reacted in situ with a diamine C (in this case (R,R)-or (S,S)-DPEN) to produce the desired transRuHCl(diphosphinite)(diamine) complexes in yields of up to 88% (Scheme 1).The yellow solid product usually consists of two diastereomers in the ratio of 2:1 for 1 and 3 and 9:1 for 2 and only one for 4. Their structures depend on the placement of the trans hydride and chloride groups relative to the folded backbone of the diphosphinite ligand. The minor isomer slowly changes to the major isomer as the product crystallizes from solution over the course of two days. The major isomer also can partly isomerize to the minor isomer when it stays in solution for more than 24 h.The structure of 3 (Fig. 1){ is similar to that of transRuHCl((R)-BINAP)((R,R)-DPEN) 18a with the PPNN atoms in the equatorial plane of a slightly distorted octahedron and with the Ru-Cl bond leaning toward the NN side. The BINOP ligand is folded over the hydride ligand. Structure determinations of BINOP-like complexes are scarce but these also have folded diphosphinite ligands. 19A comparison of complexes 1-4 as precatalysts for the asymmetric transfer hydrogenation of acetophenone by 2-propanol in the presence of KO t

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Asymmetric Hydrogenation of Ketones Using a Ruthenium(II) Catalyst Containing BINOL-Derived Monodonor Phosphorus-Donor Ligands

Cited by 69 publications

References 34 publications

Ruthenium‐Catalysed Hydrogenation of Aromatic Ketones using Monodentate Phosphoramidite Ligands

Ruthenium‐Catalysed Hydrogenation of Aromatic Ketones using Monodentate Phosphoramidite Ligands

Homogeneous Chemoselective Hydrogenation of Heterocyclic Compounds – The Case of 1,4 Addition on Conjugated C-C and C-O Double Bonds of Arylidene Tetramic Acids

A modular design of ruthenium catalysts with diamine and BINOL-derived phosphinite ligands that are enantiomerically-matched for the effective asymmetric transfer hydrogenation of simple ketones

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