Enantioselective Hydrogenation of 1-Phenyl-1,2-propanedione

Toukoniitty, Esa; Mäki‐Arvela, Päivi; Kuzma, Marek; Villela, Alexandre; Neyestanaki, Ahmad Kalantar; Salmi, Tapio; Sjöholm, Rainer; Leino, Reko; Laine, E.; Murzin, Dmitry Yu.

doi:10.1006/jcat.2001.3406

Cited by 72 publications

(55 citation statements)

References 25 publications

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“…However, when the substrate has more than one centre to be hydrogenated the reaction becomes more difficult, as occurs during the hydrogenation of diones (such as 1-phenyl-1,2-propanedione), both in terms of enantioand regioselectivity (RS). [19][20][21][22][23][24][25][26] In this case, the product of interest is (R)-1-phenyl-1-hydroxy-2-propanone, which has interesting applications in the synthesis of precursors for hypertension and asthma treatments, among others. Vol.…”

Section: Introductionmentioning

confidence: 99%

Enantioselective hydrogenation of ethyl pyruvate and 1-phenyl-1,2-propanedione on catalysts prepared by impregnation of colloidal platinum on SiO2

Ruiz¹,

Fierro²,

Reyes³

2010

J. Braz. Chem. Soc.

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A hidrogenação enantiosseletiva de piruvato de etila e de 1-fenil-1,2-propanodiona foi estudada a 298 K e sob 40 bar de H 2 sobre um catalisador de platina coloidal estabilizado com cinchonidina (CD) e suportado em sílica. O catalisador foi preparado por impregnação da platina coloidal em sílica, atingindo 1% em massa do metal no suporte. O colóide foi preparado a partir de uma solução aquosa de H 2 PtCl 6 estabilizada com diferentes quantidades de CD. O catalisador foi caracterizado por isotermas de adsorção-desorção de N 2 a 77 K e por XPS, XRD e TEM. As reações foram efetuadas em batelada em um reator de aço inoxidável, usando cicloexano como solvente e cinchonidina como modificador quiral. A adição de CD ao catalisador permite a estabilização e o controle do tamanho de partícula da platina, e também afeta o excesso enantiomérico (ee) do sistema, levando a um maior rendimento do produto com configuração R. A relação entre a concentração de CD adicionada in situ e a enantiosseletividade apresenta uma curva do tipo sino nas duas reações estudadas; este comportamento é um indicativo da importância da adsorção competitiva do modificador e do substrato na superfície do catalisador.The enantioselective hydrogenation of ethyl pyruvate and 1-phenyl-1,2-propanedione was studied at 298 K and 40 bar of H 2 over colloidal Pt stabilized with cinchonidine (CD) and supported on silica. The catalysts were prepared by impregnation of colloidal Pt on SiO 2 , leading to a metal load close to 1 wt.%. The colloid was prepared from an aqueous solution of H 2 PtCl 6 and stabilized with different quantities of CD. The catalysts were characterized by nitrogen adsorption-desorption isotherms at 77 K, XPS, XRD and TEM techniques. The reactions were carried out in a stainless steel batch reactor using cyclohexane as solvent and cinchonidine as chiral modifier. The addition of CD to the catalysts allows the stabilization and control of the platinum particle size and also affects the enantiomeric excess (ee) of the system, affording a higher proportion of the (R)-product. The relationship between the enantioselectivity and the CD concentration (added in situ) exhibits a bell type curve for both reactions, this being indicative of the importance of a competitive adsorption of the modifier and substrate on the catalyst surface.Keywords: Pt colloids, enantioselectivity, ethyl pyruvate, 1-phenyl-1,2-propanedione, cinchonidine IntroductionEnantioselective hydrogenation reactions are important tools to obtain fine chemicals used in pharmaceutical and food products.1-4 Thus, the synthesis of chiral compounds is of growing interest; among them, the hydrogenation of a-ketoesters and ketones is the most widely studied. [5][6][7][8][9][10][11][12][13][14][15] Since Orito et al. reported the enantioselective hydrogenation of ethyl pyruvate to (R)-ethyl lactate over cinchonidine-modified Pt catalysts with ee's up to 95%, many other research teams have evaluated the performance of their catalytic systems in this reaction. [16][17][18] Indeed, this is n...

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Section: Introductionmentioning

confidence: 99%

Enantioselective hydrogenation of ethyl pyruvate and 1-phenyl-1,2-propanedione on catalysts prepared by impregnation of colloidal platinum on SiO2

Ruiz¹,

Fierro²,

Reyes³

2010

J. Braz. Chem. Soc.

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“…Kinetic resolution of the primary product has also been observed in the hydrogenation of other a-diketones, a-alkoxy ketones and some activated ketones [7,[15][16][17][18]. A common feature with all of these substrates, including the structurally rigid 2-hydroxycyclohexanone [15], 2-methoxycyclohexanone [17], and 2-fluorocyclohexanone [18a], is that the (S)-enantiomer is reacting faster thus increasing the enantiomeric excess of the remaining (R)-enantiomer.…”

Section: Kinetic Resolution Of 2-hydroxy-1-indanonesmentioning

confidence: 96%

“…A common feature with all of these substrates, including the structurally rigid 2-hydroxycyclohexanone [15], 2-methoxycyclohexanone [17], and 2-fluorocyclohexanone [18a], is that the (S)-enantiomer is reacting faster thus increasing the enantiomeric excess of the remaining (R)-enantiomer. In cases where kinetic resolution of the primary hydrogenation products was observed, as in 1-phenyl-1,2-propanedione (PPD) [7], 2,3-butanedione [16,19], and cyclohexane-1,2-dione [15] hydrogenation, the minor enantiomer was converted to diols faster and the ee of the remaining hydroxyketone thus increases. Thus, in the hydrogenation of PPD in toluene the ee of (R)-1-hydroxy-1-phenyl-2-propanone is increasing from 49% at 10% of PPD conversion to 84 at full conversion (table 1).…”

Section: Kinetic Resolution Of 2-hydroxy-1-indanonesmentioning

confidence: 99%

“…Heterogeneous catalysis in turn is a method free from these disadvantages. Previously, we have investigated the enantioselective hydrogenation of 1-phenyl-1,2-propanedione (PPD) over chirally modified heterogeneous catalysts [7]. Since 1-amino-2-indanols are readily available from 2-hydroxy-1-indanone [8a] or 1,2-indandiols [8b] by the Ritter process, the chiral 1,2-indandiols themselves are important building blocks.…”

Section: Introductionmentioning

confidence: 99%

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Hydrogenation of 1,2-indanedione over heterogeneous cinchonidine-modified platinum catalysts

et al. 2007

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Hydrogenation of the prochiral diketone, 1,2-indanedione was for the first time investigated using cinchonidine-modified Pt/ Al 2 O 3 as a catalyst. The influence of the reaction parameters on catalyst activity, regio-and enantioselectivity was studied revealing fully regioselective hydrogenation of the C(2)-keto group. Enantioselectivities of the (R)-versus (S)-2-hydroxy-1-indanone varied from low to moderate in favor of the (R)-enantiomer.A systematic study of enantioselective hydrogenation of 1,2-indanedione -a new substrate for chirally modified heterogeneous catalysts -over cinchonidine modified Pt/Al 2 O 3 is presented. The influence of the reaction parameters on activity, regio-and enantioselectivity was studied.

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“…[14] Under optimal conditions, the main product, (-)-(R)-1-hydroxy-1-phenylpropan-2-one (B), has been obtained in 65 % ee using cinchonidine as the chiral catalyst modifier. The chiral hydroxy ketone B (also known as PAC = phenylacetylcarbinol) is an important intermediate for the synthesis of ephedrines and pseudoephedrines, which are major ingredients in several pharmaceuticals used as anti-asthmatics, vasoconstricting agents and nasal decongestants.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Chiral Catalyst Modifiers by Hydrosilylation of Cinchonidine and Their Application in the Hydrogenation of 1‐Phenylpropane‐1,2‐dione and Ethyl Pyruvate on a Supported Pt/Al₂O₃ Catalyst

et al. 2005

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Four new chiral modifiers were synthesized in order to investigate the effect of distal modifier substitution in the hydrogenation of ethyl pyruvate and 1-phenylpropane-1,2-dione on a supported Pt/Al 2 O 3 catalyst. The chiral modifiers were prepared in good to moderate overall yields by Pt-catalyzed hydrosilylation of 9-O-TMS-protected cinchonidine with triethylsilane, triphenylsilane, bis(dimethylsilyl)ethane and (+)-(R)-methyl(1-naphthyl)phenylsilane followed by cleavage of the silyl ether protective group. Comparison of the synthesized modifiers in enantioselective hydrogenation using cinchonidine as reference modifier is reported, as well as details on their synthesis and characterization. The X-ray crystal structure of the 11-(triphenylsilyl)-substituted cinchonidine analogue has been determined showing that this compound crystallizes in the open(3)-like conformation observed earlier for (-)-cinchonidine. In the hydrogenation of ethyl pyruvate, the new modifiers induced notable enantiomeric excesses

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Enantioselective Hydrogenation of 1-Phenyl-1,2-propanedione

Cited by 72 publications

References 25 publications

Enantioselective hydrogenation of ethyl pyruvate and 1-phenyl-1,2-propanedione on catalysts prepared by impregnation of colloidal platinum on SiO2

Enantioselective hydrogenation of ethyl pyruvate and 1-phenyl-1,2-propanedione on catalysts prepared by impregnation of colloidal platinum on SiO2

Hydrogenation of 1,2-indanedione over heterogeneous cinchonidine-modified platinum catalysts

Synthesis of Chiral Catalyst Modifiers by Hydrosilylation of Cinchonidine and Their Application in the Hydrogenation of 1‐Phenylpropane‐1,2‐dione and Ethyl Pyruvate on a Supported Pt/Al₂O₃ Catalyst

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Enantioselective Hydrogenation of 1-Phenyl-1,2-propanedione

Cited by 72 publications

References 25 publications

Enantioselective hydrogenation of ethyl pyruvate and 1-phenyl-1,2-propanedione on catalysts prepared by impregnation of colloidal platinum on SiO2

Enantioselective hydrogenation of ethyl pyruvate and 1-phenyl-1,2-propanedione on catalysts prepared by impregnation of colloidal platinum on SiO2

Hydrogenation of 1,2-indanedione over heterogeneous cinchonidine-modified platinum catalysts

Synthesis of Chiral Catalyst Modifiers by Hydrosilylation of Cinchonidine and Their Application in the Hydrogenation of 1‐Phenylpropane‐1,2‐dione and Ethyl Pyruvate on a Supported Pt/Al2O3 Catalyst

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Synthesis of Chiral Catalyst Modifiers by Hydrosilylation of Cinchonidine and Their Application in the Hydrogenation of 1‐Phenylpropane‐1,2‐dione and Ethyl Pyruvate on a Supported Pt/Al₂O₃ Catalyst