ChemInform Abstract: Asymmetric Hydrogenation of Ketones Catalyzed by Rhodium Alkyl‐AMPP Complexes: Optimized Procedure and Mechanism.

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

doi:10.1002/chin.199030098

Cited by 3 publications

(21 citation statements)

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“…The ligands are white air-sensitive powders and were characterized by microanalysis, mass spectrometry, and NMR ( 1 H, 13 C, 31 P) spectroscopies (Experimental Section) (Table ). 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.…”

Section: Resultssupporting

confidence: 75%

“…Next, unsymmetrically substituted ligands were sought. An efficient route to this class of ligands has been developed recently 12f…”

Section: Resultsmentioning

confidence: 99%

“…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. These ligands have been applied with success in asymmetric catalysis like C−C bond formation, hydroformylation, and hydrogenation of olefins and ketones . Among these bis(phosphines), we have shown that mixed ligands were the most active and selective for the hydrogenation of activated ketones. 12f,h Also we proposed that the reaction rate and the enantioselectivity of the hydrogenation were both controlled by the aminophosphine moiety 12a…”

Section: Introductionmentioning

confidence: 99%

“…These ligands have been applied with success in asymmetric catalysis like C−C bond formation, hydroformylation, and hydrogenation of olefins and ketones . Among these bis(phosphines), we have shown that mixed ligands were the most active and selective for the hydrogenation of activated ketones. 12f,h Also we proposed that the reaction rate and the enantioselectivity of the hydrogenation were both controlled by the aminophosphine moiety 12a…”

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: 75%

“…Next, unsymmetrically substituted ligands were sought. An efficient route to this class of ligands has been developed recently 12f…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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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“…For example, when the hydrogenation of benzylbenzoylformamide was run in ethanol in the presence of a cationic precatalyst, a slow reaction (t 1/2 = 4 h) with a very low ee was achieved (5.5 % ee) ( Table 1, entry 1). [32] Interestingly, if the hydrogenation occurs in ethanol in the presence of a neutral precursor, an enhanced efficiency is attained as the chiral alcohol is produced in ca. 65 % ee and with a higher rate (t 1/2 = 28 min) ( Table 1, entry 2).…”

Section: Background and Calculation Methodsmentioning

confidence: 99%

A Density Functional Study of the Hydrogenation of Ketones Catalysed by Neutral Rhodium‐Diphosphane Complexes

Agbossou‐Niedercorn

Paul

2006

Eur J Inorg Chem

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International audienceThe potential energy profile of RhI-catalysed hydrogenation of ketones has been computed for the simple model system [Rh{H3POCH2CH2N(H)PH3}(Cl)] using DFT calculations. The general sequence of the catalytic cycle involves coordination of the carbonyl derivative to the neutral RhI complex followed by oxidative addition of molecular hydrogen providing rhodium dihydride intermediates. The latter are converted into alkoxy hydrides by a migratory insertion reaction. Reductive elimination of the alcohol and substitution of the latter by the incoming substrate completes the catalytic cycle. Intermediates and transition states of all catalytic steps have been located. Two isomeric derivatives bearing the model substrate have been found for the [Rh{H3POCH2CH2N(H)PH3}(Cl)(H2CO)] complex. Eight diastereomeric pathways have been followed for the cis addition of molecular hydrogen to [Rh{H3POCH2CH2N(H)PH3}(Cl)- (H2CO)] leading to eight distinct isomeric dihydride intermediates. Four dihydride complexes can be considered as the more accessible compounds. The site preference for migratory insertion and transition states discriminates the main path of the catalytic reaction. Migratory insertion to form the alkoxy hydride constitute the turn over limiting step of the process. The potential energy profile has been found to be smooth without excessive activation barriers

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Free and Cr(CO)₃-Complexed Aminophosphine Phosphinite Ligands for Highly Enantioselective Hydrogenation of α-Functionalized Ketones

et al. 2000

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The synthesis and characterization of a new series of aryl-and cycloalkyl-substituted aminophosphine phosphinites (1-8) obtained from the reaction of the three precursors (S)-2-hydroxymethyl azetidine, (S)-3-hydroxymethyl-1,2,3,4-tetrahydroisoquinoline, and (S)-2hydroxymethylindoline and chlorophosphines is described. The aromatic ring in (S)-2hydroxymethylindoline has allowed the synthesis and isolation of tricarbonyl chromium complexed amino alcohols syn-10 and anti-10, which were similarly converted into the corresponding aminophosphine phosphinites 11-13, presenting a stereogenic center and a planar chirality. Ligand 5 ((S)-Cp,Cp-IndoNOP) revealed an unprecedented 31 P NMR fluxional behavior related to a rotation inhibition around the P-heteroatom (N and O) bonds. These new AMPP ligands were used in the enantioselective hydrogenation of various R-functionalized ketones, i.e., dihydro-4,4-dimethyl-2,3-furandione 14, N-benzyl benzoylformamide 15, ethylpyruvate 16, and 2-(N,N-dimethyl)aminoacetophenone hydrochloride 17. The stereoelectronic effects generated by the presence of the tricarbonyl chromium moiety onto the hydrogenations have been assessed. The beneficial effect of the matching chiralities in ligand syn-12 associated with the use of the most appropriate nonchiral ligand Cl has resulted in a win of 13% of ee for the rhodium-based hydrogenation of 15. While using the most suitable new chiral AMPP ligand from this study, the four above-mentioned substrates were converted into the corresponding optically active alcohols in >99% ee (l4/5), >99% ee (15/6), 87% ee (16/5), and >99% ee (17/5), respectively.

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ChemInform Abstract: Asymmetric Hydrogenation of Ketones Catalyzed by Rhodium Alkyl‐AMPP Complexes: Optimized Procedure and Mechanism.

Cited by 3 publications

References 0 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)]

A Density Functional Study of the Hydrogenation of Ketones Catalysed by Neutral Rhodium‐Diphosphane Complexes

Free and Cr(CO)₃-Complexed Aminophosphine Phosphinite Ligands for Highly Enantioselective Hydrogenation of α-Functionalized Ketones

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ChemInform Abstract: Asymmetric Hydrogenation of Ketones Catalyzed by Rhodium Alkyl‐AMPP Complexes: Optimized Procedure and Mechanism.

Cited by 3 publications

References 0 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)]

A Density Functional Study of the Hydrogenation of Ketones Catalysed by Neutral Rhodium‐Diphosphane Complexes

Free and Cr(CO)3-Complexed Aminophosphine Phosphinite Ligands for Highly Enantioselective Hydrogenation of α-Functionalized Ketones

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Free and Cr(CO)₃-Complexed Aminophosphine Phosphinite Ligands for Highly Enantioselective Hydrogenation of α-Functionalized Ketones