Enantioselective whole cell and isolated enzyme catalysed Baever-Villiger oxidation of bicyclo[3.2.0]hept-2-en-6-one

Shipston, Nigel F.; Lenn, Michael J.; Knowles, Christopher J.

doi:10.1016/0167-7012(92)90067-e

Cited by 29 publications

(14 citation statements)

References 23 publications

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“…The majority of reactions using CHMO thus far have been carried out at small scale and have used either isolated CHMO or the wild‐type whole cell as the catalyst (Shipston et al, 1992; Alphand et al, 1996; Zambianchi et al, 2000). However, these two approaches suffer from severe limitations.…”

Section: Introductionmentioning

confidence: 99%

Reactor Operation and Scale‐Up of Whole Cell Baeyer‐Villiger Catalyzed Lactone Synthesis

Doig

Avenell

Bird

et al. 2002

Biotechnology Progress

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The recombinant whole cell biocatalyst Escherichia coli TOP10 [pQR239], expressing cyclohexanone monooxygenase from Acinetobacter calcoaceticus NCIMB 9871, was used in 1.5- and 55-L fed-batch processes to oxidize bicyclo[3.2.0]hept-2-en-6-one to its corresponding regioisomeric lactones, (-)-(1S,5R)-2-oxabicyclo[3.3.0]oct-6-en-3-one and (-)-(1R,5S)-3-oxabicyclo[3.3.0]oct-6-en-2-one. By employing a bicyclo[3.2.0]hept-2-en-6-one feed rate below that of the theoretical volumetric biocatalyst activity (275 micromol x min(-1) x L(-1)), the reactant concentration in the bioreactor was successfully maintained below the inhibitory concentration of 0.2-0.4 g x L(-1). In this way approximately 3.5 g x L(-1) of the combined regioisomeric lactones was produced with a yield of product on reactant of 85-90%. The key limitation to the process was shown to be product inhibition. This process was scaled up to 55 L, producing over 200 g of combined lactone product. Using a simple downstream process (centrifugation, adsorption to activated charcoal, 5-fold concentration with ethyl acetate elution, and silica gel chromatography), we have shown that the two regioisomeric lactone products could be isolated and purified at this scale.

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Section: Introductionmentioning

confidence: 99%

Reactor Operation and Scale‐Up of Whole Cell Baeyer‐Villiger Catalyzed Lactone Synthesis

Doig

Avenell

Bird

et al. 2002

Biotechnology Progress

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“…[19] Small-scale conversions of rac-bicyclo[3.2.0]hept-2-en-6-one were carried out with TmCHMO,A cCHMO,a nd TfPAMO.B oth enantiomers of this ketone were fully converted by both CHMOs,y ielding almost exclusively one regioisomer from each enantiomer ( Figure S6A and Table S6). [20] By contrast, TfPAMO produced all four possible lactones,p roving to be far less regioselective than CHMOs.W ea lso used the same BVMOs to produce enantiomerically pure sulfoxides,w hich are widely used in asymmetric synthesis and are often biologically active. [21] Thep rochiral compound thioanisole was chosen as am odel substrate (Scheme S3).…”

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confidence: 99%

Characterization and Crystal Structure of a Robust Cyclohexanone Monooxygenase

et al. 2016

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Cyclohexanone monooxygenase (CHMO) is ap romising biocatalyst for industrial reactions owing to its broad substrate spectrum and excellent regio-, chemo-, and enantioselectivity.However,the lowstability of many BaeyerVilliger monooxygenases is an obstacle for their exploitation in industry.C haracterization and crystal structure determination of ar obust CHMO from Thermocrispum municipale is reported. The enzyme efficiently converts avariety of aliphatic, aromatic,a nd cyclic ketones,a sw ell as prochiral sulfides.A compact substrate-binding cavity explains its preference for small rather than bulky substrates.S mall-scale conversions with either purified enzyme or whole cells demonstrated the remarkable properties of this newly discovered CHMO.T he exceptional solvent tolerance and thermostability make the enzyme very attractive for biotechnology.

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“…The Baeyer-Villiger oxidation of bicydo[3.2.0]hept-2-ene-6-one (Shipston et at., 1992) and derivatives (reviewed in Faber, 1995;Roberts and Willetts, 1993) by whole cells of P. putida NCIMB 10007 (or Acinetobacter sp. NCIMB 9871) and the purified monooxygenase yields two regioisomeric lactones at high enantiomeric excess (>94% e.e.…”

Section: Iron Metabolism and Siderophores In Pseudomonas And Related mentioning

confidence: 99%

“…The (-)-isorner of bicydo[3.2.0]hept-2ene-6-one is oxidized to (-)-(IR,5S)-3-oxabicydo [3.3.0]oct-6-en-2-one, whereas the (+)-enantiomer is converted to (-)-(lS,5R)-2-oxabicydo[3.3.0]oct-6-en-3-one by a single enzyme (Fig. 4) (Shipston et at., 1992).…”

Section: Iron Metabolism and Siderophores In Pseudomonas And Related mentioning

Enantioselective whole cell and isolated enzyme catalysed Baever-Villiger oxidation of bicyclo[3.2.0]hept-2-en-6-one

Cited by 29 publications

References 23 publications

Reactor Operation and Scale‐Up of Whole Cell Baeyer‐Villiger Catalyzed Lactone Synthesis

Reactor Operation and Scale‐Up of Whole Cell Baeyer‐Villiger Catalyzed Lactone Synthesis

Characterization and Crystal Structure of a Robust Cyclohexanone Monooxygenase

Pseudomonas

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