Escherichia coli/ADH-A: An All-Inclusive Catalyst for the Selective Biooxidation and Deracemisation of Secondary Alcohols

Authors

  • Dr. Caroline E. Paul,

    1. Department of Organic and Inorganic Chemistry, University of Oviedo, Calle Julián Clavería 8, 33006 Oviedo (Spain), Fax: (+34) 985-103448
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  • Dr. Iván Lavandera,

    1. Department of Organic and Inorganic Chemistry, University of Oviedo, Calle Julián Clavería 8, 33006 Oviedo (Spain), Fax: (+34) 985-103448
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  • Dr. Vicente Gotor-Fernández,

    1. Department of Organic and Inorganic Chemistry, University of Oviedo, Calle Julián Clavería 8, 33006 Oviedo (Spain), Fax: (+34) 985-103448
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  • Prof. Wolfgang Kroutil,

    1. Department of Chemistry, Organic and Bioorganic Chemistry, University of Graz, Heinrichstrasse 28, 8010 Graz (Austria)
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  • Prof. Vicente Gotor

    Corresponding author
    1. Department of Organic and Inorganic Chemistry, University of Oviedo, Calle Julián Clavería 8, 33006 Oviedo (Spain), Fax: (+34) 985-103448
    • Department of Organic and Inorganic Chemistry, University of Oviedo, Calle Julián Clavería 8, 33006 Oviedo (Spain), Fax: (+34) 985-103448

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Abstract

The nicotinamide adenine dinucleotide regeneration system present in Escherichia coli cells was exploited for the oxidation and deracemisation of secondary alcohols with the overexpressed alcohol dehydrogenase from Rhodococcus ruber DSM 44541 (E. coli/ADH-A). Thus, various racemic alcohols were selectively oxidised with lyophilised or resting E. coli/ADH-A cells without need for an external cofactor or co-substrate. The addition of these substrates to the E. coli/ADH-A cells in buffer afforded the corresponding ketones and the remaining enantioenriched (R)-alcohols. This methodology was used for the desymmetrisation of a meso-diol and for the synthesis of the highly valuable raspberry ketone. Moreover, a biocatalytic concurrent process was developed with the resting cells of E. coli/ADH-A, ADH from Lactobacillus brevis, and glucose dehydrogenase for the deracemisation of various secondary alcohols, which afforded the desired enantiopure alcohols in more than 99 % ee starting from the racemic mixture. The reaction time of deracemisation of 1-phenylethanol was estimated to be less than 30 min. The stereoinversion of (S)-1-phenylethanol to its pure (R)-enantiomer was also achieved, which provided a biocatalytic alternative to the chemical Mitsunobu inversion reaction.

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