Utilization of cascade chemo-bio catalysis for the synthesis of R-1-phenylethyl acetate

Mäki‐Arvela, Päivi; Sahin, Serap; Kumar, Narendra; Mikkola, Jyri‐Pekka; Eränen, Kari; Salmi, Tapio; Murzin, Dmitry Yu.

doi:10.1007/s11144-008-5310-x

Cited by 6 publications

(8 citation statements)

References 7 publications

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“…In most of these studies, acetophenone 33a was transformed into (R)-1-phenylethylacetate (176) by hydrogenation using supported Pd catalysts to produce racemic 1-phenylethanol (175) followed by acylation with ethyl acetate, applying the immobilized CALB (Novozym-435) catalyst. 214,[217][218][219][220][221] In contrast to the one-pot reaction of ketoximes, in the transformation of 33a it was shown that the Pd catalyst was not efficient in the racemization step. Although optically pure 176 was obtained, the selectivity of the product did not exceeded 50%.…”

Section: View Article Onlinementioning

confidence: 99%

“…Moreover, based on results obtained using different supports, it was concluded that by-products decreased the activity of both the metal and the enzyme. 214,217,218 The sequential continuous-flow hydrogenation of 33a over Pd/SiO 2 -Al 2 O 3 and KR of 175 by immobilized CALB or crosslinked enzyme aggregates was carried out in supercritical CO 2 using consecutive reactors. 219 Later, in order to catalyse the racemization of the unreacted (S)-175, supported Ru catalyst was also introduced in the batch system, which in the absence of Pd did not promote the hydrogenation of 33a.…”

Section: View Article Onlinementioning

confidence: 99%

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Asymmetric one-pot reactions using heterogeneous chemical catalysis: recent steps towards sustainable processes

Szőllősi

2018

Catal. Sci. Technol.

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The preparation of optically pure fine chemicals is among the most important and challenging tasks met by organic chemists. Recently, significant efforts have been focused on the development of green and sustainable procedures for the synthesis of these high value-added compounds. Asymmetric heterogeneous catalysis has provided efficient solutions to these challenges. The application of heterogeneous chiral catalysts in one-pot processes combines the advantages of use of these materials with time, material, and energy savings associated with cascade or sequential procedures. This review surveys these asymmetric onepot reactions reported until July 2017, in which a heterogeneous chemical catalyst has been applied either as a single multifunctional catalyst or in combination with a second catalytically active material. These processes include one-pot procedures catalysed by carefully designed solids obtained by the immobilization of chiral metal complexes, by anchoring chiral organocatalysts, or by modifying catalytic surfaces with optically pure compounds, which may also incorporate uncatalyzed and homogeneously catalysed steps. Methods applying achiral heterogeneous catalysts in combination with soluble chiral chemical catalysts or biocatalysts are also presented. Sophisticated, finely tuned materials have been applied in most of these reactions, which have been discussed along with the main requirements necessary to perform these transformations in a one-pot manner.

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Section: View Article Onlinementioning

confidence: 99%

Section: View Article Onlinementioning

confidence: 99%

Asymmetric one-pot reactions using heterogeneous chemical catalysis: recent steps towards sustainable processes

Szőllősi

2018

Catal. Sci. Technol.

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“…In this work hydrogenation of acetophenone was carried out over 2% (w/w) Pd/N-VGCF catalysts differently pretreated. The previous studies [10,11] conducted with palladium supported on active carbon (Pd-AC) catalyst in one-pot hydrogenation of acetophenone showed that ethyl benzene was formed as a major product due to the acidic support since typically Pd/AC catalysts exhibit acidic surface groups, such as carbonyl, carboxylic, phenolic hydroxyl, lactone and quinone groups. The influence of the acid-base properties of the support on the catalytic activity has been investigated by treating oxidized VGCFs with NH 3 at different temperatures in order to introduce various amounts of basic N-containing groups on the surface.…”

Section: Hydrogenation Of Acetophenonementioning

confidence: 99%

“…The main product was ethyl benzene with a yield of 62% after 1600 min of reaction time for the preliminary experiments carried out over Pd/C and an immobilized enzyme catalyst. High ethyl benzene formation was due to the acid catalyzed dehydration by Pd/C of racemic 1phenylethanol [11]. Since the results with Pd/C catalysts were not very good due to side reactions, other Pd catalysts such as basic Pd/MgO were tested in the one-pot synthesis of (R)-1-phenylethyl acetate [10].…”

Section: Introductionmentioning

confidence: 99%

Palladium catalysts supported on N-functionalized hollow vapor-grown carbon nanofibers: The effect of the basic support and catalyst reduction temperature

Sahin

Mäki‐Arvela

Tessonnier

et al. 2011

Applied Catalysis A: General

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The basic N-functionalized vapor-grown carbon nanofibers (N-VGCF) were synthesized by post-treating oxidized VGCFs in gaseous NH3 at high temperature (ammonolysis) prior to Pd addition by sol immobilization. The catalysts were characterized by nitrogen adsorption, hydrogen temperature programmed desorption, adsorption microcalorimetry and by SEM and TEM. Catalytic activity was evaluated in a model reaction, synthesis of (R)-1-phenylethyl acetate starting from hydrogenation of acetophenone to racemic 1-phenylethanol over Pd supported on N-VGCFs, at 70 °C under atmospheric hydrogen pressure in toluene, followed by acylation over an immobilized lipase in the same reaction pot. The main parameters investigated in this work were the role of the basic N-VGCF supports as well as the reduction procedure of the supported Pd catalysts (Pd-N-VGCF). The results revealed that the catalytic activity of the Pd-N-VGCF catalysts was highly dependent on the reduction procedure. The highest desired product yield, 35%, was obtained over a Pd-N-VGCF catalyst when the support was treated at 400 °C with gaseous ammonia prior to Pd addition.

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“…Hydrogenation and kinetic resolution in one-pot can be achieved by use of a low acidity Pd/Al 2 O 3 catalyst for hydrogenation and an immobilized lipase for resolution [3][4][5][6]. The drawback in this approach was, however, the lack of racemization step, which limiting the yield of the desired product to 50%.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of the chemo–bio catalyzed cascade synthesis of R-1-phenylethyl acetate over Pd/Al2O3, lipase, and Ru-catalysts

et al. 2010

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One-pot synthesis of R-1-phenylethyl acetate was investigated starting from acetophenone hydrogenation performed over Pd/Al 2 O 3 and PdZn/Al 2 O 3 catalysts followed by acylation of the intermediate secondary alcohol, R-1-phenylethanol, over an immobilized lipase. Furthermore, the performance of a third type of catalyst, Ru supported on hydroxyapatite (HAP) was evaluated for racemization of S-1-phenylethanol in one pot together with the two other catalysts. The main objectives of this work were to separate the effects of different catalysts and to reveal the reaction mechanism. For this purpose not only acetophenone, but also (R,S)-1-phenylethanol, S-1-phenylethanol, R-1-phenylethyl acetate, and styrene were used as reactants in combination with Pd/Al 2 O 3 , lipase and Ru/HAP as catalysts. The results revealed that the main side product, ethylbenzene, was formed in two different ways, via dehydration of (R,S)-1-phenylethanol to styrene, followed by its rapid hydrogenation to ethylbenzene, and via debenzylation of the desired product, R-1-phenylethyl acetate to ethylbenzene. The true one-pot synthesis, however, was demonstrated over Shvo's catalyst, but Ru/HAP was not sufficiently active in the racemization step. Ru/Al 2 O 3 was a promising catalyst for racemization of S-1-phenylethanol and for dynamic kinetic resolution of (R,S)-1-phenylethanol, when using only small amounts of the acyl donor ethyl acetate. The challenge in

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Utilization of cascade chemo-bio catalysis for the synthesis of R-1-phenylethyl acetate

Cited by 6 publications

References 7 publications

Asymmetric one-pot reactions using heterogeneous chemical catalysis: recent steps towards sustainable processes

Asymmetric one-pot reactions using heterogeneous chemical catalysis: recent steps towards sustainable processes

Palladium catalysts supported on N-functionalized hollow vapor-grown carbon nanofibers: The effect of the basic support and catalyst reduction temperature

Mechanism of the chemo–bio catalyzed cascade synthesis of R-1-phenylethyl acetate over Pd/Al2O3, lipase, and Ru-catalysts

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