Asymmetric hydrogenation of activated keto compounds catalyzed by new chiral peralkyl-ampp rhodium complexes

Hatat, Corinne; Karim, Abdallah; Kokel, N.; Mortreux, André; Petit, François

doi:10.1016/s0040-4039(00)82151-6

Cited by 26 publications

(5 citation statements)

References 10 publications

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“…Their NMR properties resemble those described earlier for the corresponding aminophosphine−phosphinite ligands 12f. Thus, ligands ( S )- 1 − 10 exhibited two 31 P resonances that were assigned on the basis of chemical shifts trends established earlier (Table ) 9a. Generally, for amidophosphine−phosphinites, the chemical shifts of the PN (36−60.9 ppm) and PO moieties (114.4−150.4 ppm) were downfield from those of the analogous aminophosphine−phosphinite ligands.…”

Section: Resultssupporting

confidence: 78%

“…Synthesis and Characterization of Amidophosphine − Phosphinite Ligands. Symmetrically substituted aminophosphine−phosphinite ligands are generally synthesized by reaction of an amino alcohol with the appropriate chlorophosphine 9a…”

Section: Resultsmentioning

confidence: 99%

“…We have conducted an extensive study of the synthesis of new chiral diphosphines in order to apply them in asymmetric catalysis. For that purpose, special efforts have been devoted toward the synthesis of easily accessible ligands based on natural amino acids and amino alcohols . Accordingly, the synthesis of several chiral aminophosphine− and amidophosphine−phosphinite ligands (abbreviated AMPP) bearing either identical or different substituents at their phosphorus atoms has been presented.…”

Section: Introductionmentioning

confidence: 99%

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Amidophosphine−Phosphinites: Synthesis and Use in Rhodium-Based Asymmetric Hydrogenation of Activated Keto Compounds. Crystal Structure of Bis[(μ-chloro)((S)-2-((diphenylphosphino)oxy)-2-phenyl-N-(diphenylphosphino)-N-methylacetamide)rhodium(I)]

et al. 1996

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Amidophosphine−phosphinite ligands (AMPP) derived from (S)-N-benzylmandelamide ((S)-R,R‘-benzylmandelNOP (S)-1 (R = R‘ = phenyl) and (S)-7 (R = phenyl, R‘ = cyclopentyl)), (S)-N-methylmandelamide ((S)-R,R‘-methylmandelNOP (S)-2 (R = R‘ = phenyl) and (S)-8 (R = phenyl, R‘ = cyclopentyl)), (S)-N-methyllactamide ((S)-R,R‘-methyllactaNOP (S)-3 (R = R‘ = phenyl) and (S)-9 (R = phenyl, R‘ = cyclopentyl)), and (S)-2-(hydroxymethyl)-2-pyrrolidinone ((S)-R,R‘-oxoProNOP (S)-4−6 and (S)-10 (R, R‘ = phenyl, cyclohexyl, cyclopentyl)) have been prepared in high yields (60−94%) and reacted with rhodium precursors to prepare neutral “Rh{AMPP}” complexes 11−26 of general formula [Rh{AMPP}X]2, where X = Cl, I, OCOCH3, OCOCF3, and OCOC3F7. The crystal structure of [Rh{(S)-Ph,Ph-methylmandelNOP}Cl]2 (12) has been determined. The rhodium atom has a cis square-planar coordination, and the seven-membered chelate ring has a boat conformation with the nitrogen atom in the mean plane RhP2. Complexes 11−26 have been used as catalyst precursors for the asymmetric hydrogenation of dihydro-4,4-dimethyl-2,3-furandione (27) and N-benzylbenzoylformamide (29) giving the corresponding optically active hydroxy compounds 28 and 30 in high yields and low to high enantiomeric excesses (28−98.7% ee and 13−87% ee, respectively). Catalytic activities (turnover frequency at 50% conversion at room temperature up to 3300 h-1) as well as the enantioselectivities depended strongly on the nature of the substituents on phosphorus as well as on the nature of the non chiral ligands. Catalyst precursor [Rh{(S)-Cp,Cp-oxoProNOP}OCOCF3]2 afforded (R)-pantolactone in 98.7% ee.

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Section: Resultssupporting

confidence: 78%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Amidophosphine−Phosphinites: Synthesis and Use in Rhodium-Based Asymmetric Hydrogenation of Activated Keto Compounds. Crystal Structure of Bis[(μ-chloro)((S)-2-((diphenylphosphino)oxy)-2-phenyl-N-(diphenylphosphino)-N-methylacetamide)rhodium(I)]

et al. 1996

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“…As stated above, the preparation of this type of ligand is usually a complicated process. Illustrative examples are (S)-BINAPO, 17 cophinite, 18 ProNOP, 19 valNOP, 20 and alaNOP, 21 or ProNOP 22 derivatives. In the synthesis of these ligands the last step, where the phosphinite functional group is generated, involves the reaction of an alcohol with a phosphorus derivative under very harsh conditions.…”

Section: Resultsmentioning

confidence: 99%

Ruthenium Arene Derivatives with PN Hemilabile Ligands. P−C Cleavage and Phosphine to Phosphinite Transformation

et al. 2004

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Complexes of formula [RuCl 2 (arene)(κ 1 -dpim)] (dpim ) 2-(diphenylphosphino)-1-methylimidazole) (arene ) p-cymene, 1a; C 6 H 6 , 1b) were prepared by the reaction of [RuCl 2 (pcymene)] 2 or [RuCl 2 (C 6 H 6 )(CH 3 CN)] with dpim. Complexes 1a and 1b were structurally characterized by NMR spectroscopy and X-ray diffraction. The reaction of these precursors with BF 4salts led, in dichloromethane, to cationic complexes of formula [RuCl(arene)(κ 2dpim)]BF 4 (arene ) p-cymene, 2a; C 6 H 6 , 2b). However, in methanol the products were unexpected phosphinite derivatives of the type [RuCl(arene)(HImMe){κ 1 -PPh 2 (OMe)}]A (A ) BF 4 , arene ) p-cymene, 3a; C 6 H 6 , 3b; A ) BPh 4 , arene ) p-cymene, 3d) (ImMe ) methylimidazole). This transformation implies the existence of an easy P-C bond cleavage and phosphine functionalization with methanol at room temperature. The precursors 1a,b or the analogous derivative with 2-(diphenylphosphino)pyridine (PPh 2 py), [RuCl 2 (p-cymene)-(κ 1 -PPh 2 py)], 1c, reacted with HBF 4 to give cationic derivatives by protonation of the imidazole or the pyridine fragment, [RuCl 2 (arene)(κ 1 -PNH)]BF 4 (PNH ) dpimH, arene ) p-cymene, 4a; C 6 H 6 , 4b; PNH ) PPh 2 pyH, arene ) p-cymene, 4c). In these compounds the existence of an asymmetric and bifurcated hydrogen bond NH‚‚‚Cl 2 has been structurally determined (even by X-ray studies for 4a,b). Complexes 2a and 4a also yield the corresponding and analogous phosphinite derivatives in the presence of methanol-d 4 but at a markedly slower rate. NMR and spectrophotometric studies provided information concerning the formation of the phosphinite derivatives. It was concluded that the phosphine is not functionalized if it is not coordinated and that, very probably, a methanol solvatesintermediate between 1a and 2asparticipates in the P-C bond cleavage and allows the aforementioned transformation. Some preliminary catalytic tests involving the transfer hydrogenation of cyclohexanone and the hydrogenation of phenylacetylene have also been carried out.

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“…Development of synthetic methods for α-hydroxyamides has attracted considerable interest, since they include valuable therapeutic agents and also possess synthetic utility. General routes to α-hydroxyamides include: (i) the reduction of α-keto-amides with sodium borohydride, with other metal borohydrides, such as LiBEt 3 H, KBEt 3 H, and Zn(BH 4 ) 2 23 or with magnesium- or titanium-based reagents; (ii) the hydrogenation of α-keto-amides in the presence of palladium on charcoal or neutral rhodium (I) complexes; (iii) the oxidation of acyclic, tetra-substituted amide-enolates by oxaziridines with yields of around 50% . Methods i and ii need α-keto-amides prepared, e.g., from α-ketoacids 22b or α-keto-acyl chlorides 22c.…”

Section: Resultsmentioning

confidence: 99%

N-Acylbenzotriazoles: Neutral Acylating Reagents for the Preparation of Primary, Secondary, and Tertiary Amides

2000

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Asymmetric hydrogenation of activated keto compounds catalyzed by new chiral peralkyl-ampp rhodium complexes

Cited by 26 publications

References 10 publications

Amidophosphine−Phosphinites: Synthesis and Use in Rhodium-Based Asymmetric Hydrogenation of Activated Keto Compounds. Crystal Structure of Bis[(μ-chloro)((S)-2-((diphenylphosphino)oxy)-2-phenyl-N-(diphenylphosphino)-N-methylacetamide)rhodium(I)]

Amidophosphine−Phosphinites: Synthesis and Use in Rhodium-Based Asymmetric Hydrogenation of Activated Keto Compounds. Crystal Structure of Bis[(μ-chloro)((S)-2-((diphenylphosphino)oxy)-2-phenyl-N-(diphenylphosphino)-N-methylacetamide)rhodium(I)]

Ruthenium Arene Derivatives with PN Hemilabile Ligands. P−C Cleavage and Phosphine to Phosphinite Transformation

N-Acylbenzotriazoles: Neutral Acylating Reagents for the Preparation of Primary, Secondary, and Tertiary Amides

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