Transformation of racemic ethyl 3-hydroxybutanoate into the (R)-enantiomer exploiting lipase catalysis and inversion of configuration

Turcu, Mihaela C.; Kiljunen, Eero; Kanerva, Liisa T.

doi:10.1016/j.tetasy.2007.06.030

Cited by 17 publications

(7 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Therefore, in order to increase the overall yield as well as the economy of the process, the configuration inversion of the coproducts ethyl (S)-hydroxybutyrate 2 and (S)-3-hydroxybutyl acetate 5 was then taken into account. The inversion of (S)-to (R)-2 by mesylation of the hydroxyl group followed by SN2 with cesium acetate has been recently published [26]. However, a following work reported a low selectivity of this procedure because of the formation of ethyl 3-methylacrylate as elimination by-product [24].…”

Section: Inversion Of Configuration Of (S)-3-hydroxybutyl Acetatementioning

confidence: 99%

An Alternative Enzymatic Route to the Ergogenic Ketone Body Ester (R)-3-Hydroxybutyl (R)-3-Hydroxybutyrate

Zaccone¹,

Venturi²,

Giovannini³

et al. 2020

Preprint

View full text Add to dashboard Cite

The oral administration of (R)-3-hydroxybutyl-(R)-3-hydroxybutyrate, allows inducing a beneficial level of blood ketone bodies without the adverse effects due to the adhesion to a ketogenic diet. Several studies documented the therapeutic effectiveness of the (R)-3-hydroxybutyl (R)-3-hydroxybutyrate in treating neurodegenerative diseases as well as its boosting activity of athletic and cognitive performances during prolonged physical exercises. Further studies considering this ketone body ester for therapy of other pathologies are also underway. In the present work, we describe the synthesis of (R)-3-hydroxybutyl-(R)-3-hydroxybutyrate through the enantioselective transesterification of racemic ethyl 3-hydroxybutyrate with (R)-1,3-butanediol catalyzed by immobilized Candida antarctica lipase B (CAL-B). The enantiopure (R)-1,3-butanediol was in turn obtained from the kinetic resolution of the racemate by CAL-B catalyzed acetylation with vinyl acetate. The economy of the synthetic procedure has been improved by recycling the unreacted (S) enantiomers of the ethyl 3-hydroxybutyrate and 1,3-buatnediol after stereochemical inversion achieved by tosylation and SN2 with ammonium acetate. The overall procedure allows to incorporate up to 70% of the starting racemic reagents into the final product.

show abstract

Section: Inversion Of Configuration Of (S)-3-hydroxybutyl Acetatementioning

confidence: 99%

An Alternative Enzymatic Route to the Ergogenic Ketone Body Ester (R)-3-Hydroxybutyl (R)-3-Hydroxybutyrate

Zaccone¹,

Venturi²,

Giovannini³

et al. 2020

Preprint

View full text Add to dashboard Cite

show abstract

“…The β-keto esters is one of the most studied classes of compounds in enantioselective reactions (Mori, 1989;Nakamura et al, 1995;North, 1996;Salvi and Chattopadhyay, 2004;Spiliotis et al, 1990;Turcu et al, 2007;Ushio et al, 1991). Its products, β -hydroxy esters, are extremely useful as building blocks for the synthesis of a large number of bioactive compounds, intermediates and chiral auxiliaries (Ishihara et al, 2003;Salvi and Chattopadhyay, 2006).…”

Section: Reduction Of Ethyl Acetoacetate (2)mentioning

confidence: 99%

Bioreduction of Some Common Carbonylic Compounds Mediated by Yeasts

Silva

Alarcón

Águila

et al. 2010

Zeitschrift Für Naturforschung C

View full text Add to dashboard Cite

Bioreduction of several prochiral carbonylic compounds such as acetophenone (1), ethyl acetoacetate (2) and ethyl phenylpropionate (3) to the corresponding optically active secalcohols 1a -3a was performed using wild-type strains of Pichia pastoris UBB 1500, Rhodotorula sp., and Saccharomyces cerevisiae. The reductions showed moderate to excellent conversion and high enantiomeric excess, in an extremely mild and environmentally benign manner in aqueous medium, using glucose as cofactor regeneration system. The obtained alcohols follow Prelog's rule, but in the reduction of 1 with P. pastoris UBB 1500 the antiPrelog enantiopreference was observed.

show abstract

“…Lipase-catalyzed access to the enantiomers of rac-1 was previously achieved by catalysis with Candida antarctica lipase B (Novozym 435). [10] The kinetic resolution of rac-2, rac-cis-3, and rac-cis-4 is now considered. In a broader context, we have focused on the possibility of preparing the four stereoisomers of 3 and also studied the lipase-catalyzed acylation of rac-trans-3.…”

Section: 6-dihydro-4-hydroxy-6-methyl-4h-thieno[23-b]thiopyran 77mentioning

confidence: 99%

“…[11] Later, the development of a lipase-catalyzed solvent-free process combined with mesylation and subsequent acylation with caesium acetate allowed an easy and clean access to the acylated ethyl (R)-3-hydroxybutanoate from rac-1. [10] In addition, dynamic kinetic resolution methods, which allow the transformation of a racemic mixture into the more reactive enantiomer, have been widely investigated. [12] When an enantiopure alcohol contains two or more asymmetric centers the resolution methods can lead to a mixture of enantiopure diastereomers.…”

Section: 6-dihydro-4-hydroxy-6-methyl-4h-thieno[23-b]thiopyran 77mentioning

confidence: 99%

Applying Lipase Catalysis to Access the Enantiomers of Dorzolamide Intermediates

2009

Self Cite

View full text Add to dashboard Cite

The kinetic resolution of three dorzolamide intermediates has been studied in the presence of Burkholderia cepacia lipase in organic solvents. All the stereoisomers of 6-methyl-5,6-dihydro-4H-thieno[2,3-b]thiopyran-4-ol were prepared starting from the racemic cis-dihydrothiopyranol intermediate giving first the 4R,6S and 4S,6R enantiomers. Subsequent epimerization and purification of the trans enantiomers by enzymatic acylation or alcoholysis then gave the cis enantio-

show abstract

Transformation of racemic ethyl 3-hydroxybutanoate into the (R)-enantiomer exploiting lipase catalysis and inversion of configuration

Cited by 17 publications

References 18 publications

An Alternative Enzymatic Route to the Ergogenic Ketone Body Ester (R)-3-Hydroxybutyl (R)-3-Hydroxybutyrate

An Alternative Enzymatic Route to the Ergogenic Ketone Body Ester (R)-3-Hydroxybutyl (R)-3-Hydroxybutyrate

Bioreduction of Some Common Carbonylic Compounds Mediated by Yeasts

Applying Lipase Catalysis to Access the Enantiomers of Dorzolamide Intermediates

Contact Info

Product

Resources

About