Enantioselective reduction of ortho-substituted acetophenones by bacterial strains isolated from medium enriched with biphenyl or diesel fuel

doi:10.1016/j.molcatb.2005.02.003

Journal of Molecular Catalysis B: Enzymatic

Volume 33, Issues 3–6, 1 June 2005, Pages 73-79

https://doi.org/10.1016/j.molcatb.2005.02.003 Get rights and content

Abstract

Application of 21 new bacterial strains from natural environments (coastal plain of Santos and Atlantic Rain Forest, São Paulo, Brazil) in the asymmetric reduction of acetophenone derivatives is described. The bioreduction was carried out with whole bacterial cells leading to (S)-chiral alcohols in up to ≥99% e.e. The (S)-(−)-1-(2-bromo-phenyl)-ethanol was employed in the preparation of chiral tellurium derivatives.

Introduction

Biocatalysis is one of the most important scientific topics in Green Chemistry in which materials are expected to be used efficiently, emissions and waste production reduced and inherently safe process sought [1]. In addition to this concern, the growing interest in the synthesis of chiral molecules in enantiomerically pure form has also promoted a great development in biocatalysis [2], [3]. Among the compounds of interest, chiral alcohols have been prepared by reduction of aromatic ketones by fungi, bacteria and isolated enzymes as biocatalyst. The biocatalytic reactions can be carried out using whole microbial cells or isolated enzymes. In the case of isolated dehydrogenases the external addition of expensive coenzymes and a recycling system are required what confer to this protocol some economical disadvantages. In this way screening for new microorganisms strains isolated from different natural environments are used in the search for efficient enzymatic systems, which can promote the biotransformation with no need of external additives [4]. In view of the vast diversity of the Brazilian biomes we initiated a study aiming to explore microorganisms isolated from them in ketone reductions and alcohol deracemizations. Initially new fungi strains were studied for this purpose [5]. In this communication we report a study on the potential of new bacterial strains isolated from coastal plain and forest areas of São Paulo state (Brazil) as enantioselective reducing agents for acetophenone derivatives.

Section snippets

General methods

2′-Bromoacetophenone, 3′-bromoacetophenone, 4′-bromoacetophenone, 2′-chloroacetophenone, 3′-chloroacetophenone, 4′-chloroacetophenone, 2′-fluoroacetophenone and 2′-nitroacetophenone are commercially available and were used without further purification. 2′-Methylselenoacetophenone and 2′-phenylselenoacetophenone were prepared according to previous report [5b]. Thin-layer chromatography (TLC) was performed using precoated plates (Aluminum foil, silica gel 60 F₂₅₄ Merck, 0.25 mm). Merck 60 silica

Isolation of the bacterial strains

The isolates were obtained after an enrichment procedure, carried out through the inoculation of sampled sediment (1.0 g) in flasks containing a mineral salt medium and diesel fuel (0.05%) or biphenyl crystals (100 mg) as carbon source [7], [8]. The cultures were incubated in an orbital shaker (160 rpm; 28 °C) until growth was observed, followed by three serial transfers and isolation in solid medium. The identification of part of the isolates was performed through 16S rDNA gene sequencing and

Conclusion

In summary, several bacterial strains isolated from medium enriched with biphenyl or diesel fuel can be used to perform efficient enantioselective reduction of ortho-substituted acetophenones to their corresponding chiral (S)-alcohols. The chiral products can be employed in the preparation of chiral tellurium derivatives.

Acknowledgements

The authors are grateful to E. Kagohara for technical assistance. A.L.M. Porto, L.H. Andrade and D.F. Rodrigues thank FAPESP for fellowships. J.V. Comasseto and V.H. Pellizari thank FAPESP and CNPq for support.

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Enantioselective reduction of ortho-substituted acetophenones by bacterial strains isolated from medium enriched with biphenyl or diesel fuel

Abstract

Introduction

Section snippets

General methods

Isolation of the bacterial strains

Conclusion

Acknowledgements

Curr. Opin. Biotechnol.

Curr. Opin. Biotechnol.

Nature

Appl. Environ. Microbiol.

Pure Appl. Chem.

J. Org. Chem.

Tetrahedron Lett.

Chem. Rev.