Biocatalytic separation of (R, S)-1-phenylethanol enantiomers and fractionation of reaction products with supercritical carbon dioxide

Paiva, Alexandre; Vidinha, Pedro; Angelova, Maria; Rebocho, Sílvia; Barreiros, Susana; Brunner, Gerd

doi:10.1016/j.supflu.2010.09.037

Cited by 17 publications

(13 citation statements)

References 26 publications

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“…[3] The special advantages of using supercritical carbon dioxide as a solvent are its beneficial properties in product separation. [4] The enzyme catalysed kinetic resolution of 1-phenylethanol is a widely studied model reaction.…”

Section: Introductionmentioning

confidence: 99%

“…These reactions have been studied in organic solvents [5,6], in supercritical carbon dioxide (scCO2) [4,7], in ionic liquids [8,9], an in a scCO2/ionic liquid biphasic system [10].…”

Section: Introductionmentioning

confidence: 99%

“…Vinyl butyrate was selected as optimal esterification agent regarding the reaction rate maximisation under atmospheric conditions. [4,10] Although vinyl esters are advantageous, because the…”

Section: Introductionmentioning

confidence: 99%

“…equilibrium is shifted towards the formation the products by the immediate oxo-enol tautomerisation of the vinyl alcohol to acetaldehyde [15], vinyl acetate is highly volatile resulting in obvious environmental effects and losses and downstream processing [4,16] might also be problematic. Due to the wide acceptable substrate range of the popular lipases, as…”

Section: Introductionmentioning

confidence: 99%

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One pot kinetic resolution and product separation with corn germ oil and supercritical carbon dioxide

Kmecz

Varga

Székely

2018

The Journal of Supercritical Fluids

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Section: Introductionmentioning

confidence: 99%

“…These reactions have been studied in organic solvents [5,6], in supercritical carbon dioxide (scCO2) [4,7], in ionic liquids [8,9], an in a scCO2/ionic liquid biphasic system [10].…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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One pot kinetic resolution and product separation with corn germ oil and supercritical carbon dioxide

Kmecz

Varga

Székely

2018

The Journal of Supercritical Fluids

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“…Reetz et al [7] and Lozano et al [6] combined kinetic resolution in ionic liquids with extraction with supercritical carbon dioxide (scCO 2 ), to avoid the use of organic solvents in the separation step. Paiva et al [8] followed a similar approach to that of Reetz et al [7] in what concerns the choice of an acylating agent leading to an ester product differing considerably in size and thereby easier to separate from unreacted alcohol. In this case, scCO 2 was used simultaneously as a solvent in the enzymatic reaction and subsequent fractionation of the reaction mixture exiting the reactor.…”

Section: Introductionmentioning

confidence: 99%

High pressure vapor–liquid equilibrium for the ternary system ethanol/(±)-menthol/carbon dioxide

Rebocho

Nunes

Najdanovic‐Visak

et al. 2014

The Journal of Supercritical Fluids

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PEG₆₀₀‐Carboxylates as Efficient Reusable Reaction Media and Acylating Agents for the Resolution of sec‐Alcohols

et al. 2014

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Herein is presented a simple, attractive, and reusable methodology for one-pot resolution/separation of free sec-alcohols with enantiomeric excess (ee) values over 90 % by the combination of sustainable acylating agents/solvents (polyethylene glycol derivatives) and an easily available and common biocatalyst (Candida antarctica lipase B, or CAL B) under irreversible conditions, along with a separation process by extraction or distillation. A scale-up reaction was carried out with the Fluoxetine precursor with ee values close to 90 % for the R enantiomer.Enantiomerically pure sec-alcohols are an important class of biologically relevant compounds amenable to facile and selective functional-group transformation. Stereoselective synthesis of a desired enantiomer can be achieved through asymmetric reduction of ketones, stereoselective nucleophilic addition to aldehydes, dynamic kinetic resolution of racemic sec-alcohols, and modification of enantiomeric natural products available from the chiral pool.Resolution of racemic alcohols is an appealing strategy, particularly when both enantiomers are valuable. Standard chromatographic methods such as chiral high-performance liquid chromatography (HPLC) and gas-liquid chromatography (GLC) excel for analytical purposes and small-scale preparative purposes but are not viable for any meaningful scale-up. Simulated moving-bed chromatography has allowed for continuous operation but the high cost of chiral stationary phases and need for careful optimization for each substrate has reserved this method for more intensive resolutions.[1] Membrane technology using chiral selectors is another continuous resolution method.[2] Crystallization has been the standard for racemic resolution, particularly for substrates that can form organic salts, such as amines and carboxylic acids. By contrast, the formation of inclusion complexes is the only described method for resolution of sec-alcohols by crystallization.[3]The preferred method for sec-alcohol resolution has been kinetic resolution (KR). There are a few instances of chemical KR methods, [4] but the majority of applications focus on the enzymatic kinetic resolution (EKR), either by acylation of an alcohol or by hydrolysis of the acylated product. EKR is a well-established method given that the biocatalysts employed accept a broad range of substrates and afford very high enantioselectivity. The success of an EKR is dependent on three factors: 1) high efficiency of the enzyme, the stability of which can be increased in selected organic solvents, ionic liquids (ILs), [5] and eutectic solvents; [6] 2) the occurrence of EKR under irreversible conditions achieved by either using vinyl esters or anhydrides as acylating agents, [7] or drying agents for water removal or product removal (water or volatile alcohol) by evaporation under vacuum; [8] and 3) effective separation of the two enantiomers as free alcohol and ester.[9] The separation step is an important factor for upscaling a process. Separation methods are based on the type of acylati...

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Biocatalytic separation of (R, S)-1-phenylethanol enantiomers and fractionation of reaction products with supercritical carbon dioxide

Cited by 17 publications

References 26 publications

One pot kinetic resolution and product separation with corn germ oil and supercritical carbon dioxide

One pot kinetic resolution and product separation with corn germ oil and supercritical carbon dioxide

High pressure vapor–liquid equilibrium for the ternary system ethanol/(±)-menthol/carbon dioxide

PEG₆₀₀‐Carboxylates as Efficient Reusable Reaction Media and Acylating Agents for the Resolution of sec‐Alcohols

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Biocatalytic separation of (R, S)-1-phenylethanol enantiomers and fractionation of reaction products with supercritical carbon dioxide

Cited by 17 publications

References 26 publications

One pot kinetic resolution and product separation with corn germ oil and supercritical carbon dioxide

One pot kinetic resolution and product separation with corn germ oil and supercritical carbon dioxide

High pressure vapor–liquid equilibrium for the ternary system ethanol/(±)-menthol/carbon dioxide

PEG600‐Carboxylates as Efficient Reusable Reaction Media and Acylating Agents for the Resolution of sec‐Alcohols

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PEG₆₀₀‐Carboxylates as Efficient Reusable Reaction Media and Acylating Agents for the Resolution of sec‐Alcohols