A “Designer Yeast” That Catalyzes the Kinetic Resolutions of 2-Alkyl-Substituted Cyclohexanones by Enantioselective Baeyer−Villiger Oxidations

Stewart, Jon D.; Reed, Kieth W.; Zhu, Junwen; Chen, Gang; Kayser, Margaret M.

doi:10.1021/jo961028p

Cited by 84 publications

(31 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Among the ketones used in this study, compounds 1 to 5 ( Fig. 3) are available commercially (Aldrich); the remaining ones were prepared as described previously (38,48,62,72).…”

Section: Methodsmentioning

confidence: 99%

“…The new whole-cell engineered systems circumvented the potentially pathogenic Acinetobacter sp. in biotransformation, in addition to producing lactones with very high enantioselectivities in asymmetric BV oxidations of a large number of ketones (38,48,62). Another notable aspect of overexpression of a clone of CHMO in E. coli was the sequence determination by mass spectrometry (40) that confirmed the DNA-predicted sequence reported by Iwaki et al (32).…”

mentioning

confidence: 99%

See 1 more Smart Citation

Cloning and Characterization of a Gene Cluster Involved in Cyclopentanol Metabolism in Comamonas sp. Strain NCIMB 9872 and Biotransformations Effected by Escherichia coli -Expressed Cyclopentanone 1,2-Monooxygenase

Iwaki

Hasegawa

Wang

et al. 2002

Appl Environ Microbiol

Self Cite

124

View full text Add to dashboard Cite

54 -dependent regulatory elements in front of the divergently transcribed cpnB and cpnC genes supports the notion that cpnR is a regulatory gene of the NtrC type. Knowledge of the nucleotide sequence of the cpn genes was used to construct isopropyl-␤-thio-D-galactoside-inducible clones of Escherichia coli cells that overproduce the five enzymes of the cpn pathway. The substrate specificities of CpnA and CpnB were studied in particular to evaluate the potential of these enzymes and establish the latter recombinant strain as a bioreagent for Baeyer-Villiger oxidations. Although frequently nonenantioselective, cyclopentanone 1,2-monooxygenase was found to exhibit a broader substrate range than the related cyclohexanone 1,2-monooxygenase from Acinetobacter sp. strain NCIMB 9871. However, in a few cases opposite enantioselectivity was observed between the two biocatalysts.Pseudomonas sp. strain NCIMB 9872, which is capable of growth on 0.1% cyclopentanol as sole carbon source, was isolated from a freshwater stream in Illinois by P. J. Chapman some three decades ago. Trudgill and coworkers (27) used this strain as a prototype organism to establish the biochemical pathway of cyclopentanol metabolism shown in Fig. 1. For reason of utility as a Baeyer-Villiger (BV) biocatalyst and its mechanistic aspects (2,8,13,58,71), the second biochemical step catalyzed by cyclopentanone 1,2-monooxygenase (CPMO) has been most extensively studied in this organism. The conversion of cyclopentanone to 5-valerolactone is NADPH and flavin adenine dinucleotide (FAD) dependent, and CPMO has been purified to near homogeneity. It is a tetramer of subunit molecular weight 50,000 to 54,000 (8,66). Assay of the FAD/ protein ratio gave values of 2 to 4 molecules of FAD bound to each tetrameric enzyme molecule (28,66). An N-terminal 29-amino-acid sequence of CPMO has been determined (8).A chemical BV oxidation is the transformation of ketones into esters or of cyclic ketones into lactones by peracids, such as 3-chloroperbenzoic acid. This century-old reaction (for reviews, see references 54 and 63) continues to attract interest not only in broadening the spectrum of applications (ranging from the synthesis of steroids, antibiotics, and pheromones to the synthesis of monomers for polymerization, etc.) but also in developing oxidants that are more chemoselective and efficient and thus result in more product than waste (20).The biological BV reactions catalyzed by BV monooxygenases (BVMOs) offer the prospect of eco-efficient chemical transformations in whole cells or improved expression systems via cloning. Moreover, BVMOs can provide products in optically active form which are difficult to obtain by other strategies (for reviews, see references 55, 61, 71, and 74). Notable ste-* Corresponding author. Mailing address:

show abstract

“…Among the ketones used in this study, compounds 1 to 5 ( Fig. 3) are available commercially (Aldrich); the remaining ones were prepared as described previously (38,48,62,72).…”

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

Cloning and Characterization of a Gene Cluster Involved in Cyclopentanol Metabolism in Comamonas sp. Strain NCIMB 9872 and Biotransformations Effected by Escherichia coli -Expressed Cyclopentanone 1,2-Monooxygenase

Iwaki

Hasegawa

Wang

et al. 2002

Appl Environ Microbiol

Self Cite

124

View full text Add to dashboard Cite

show abstract

“…[106] Many cyclic ketones in agreement with Hawthorne and EmmonsЈ conclusion". [83] are oxidized by the cyclohexanone oxygenase isolated from the bacteria Acinetobacter NCIB 9871, [107Ϫ109] or by modiWhereas the effect of strong acids (trifluoroperacetic acid, dichloroperacetic acid, or sulfuric acid) and the influ-fied yeast [110] as well as by microorganisms.…”

Section: The Kinetics Of the Baeyer؊villiger Reactionmentioning

confidence: 99%

100 Years of Baeyer–Villiger Oxidations

Renz

Meunier²

1999

Eur. J. Org. Chem.

542

307

View full text Add to dashboard Cite

In the present review, we report the discovery of the formation of esters and lactones by oxidation of ketones with a peroxide derivative, namely the Baeyer–Villiger reaction. This reaction was first reported by Adolf von Baeyer and Victor Villiger a century ago in 1899, just one year after the oxidant they used (KHSO5) has been described. Furthermore, Baeyer and Villiger established the composition of this new inorganic peroxide and showed that its instability was the reason of a controversy between several European chemists between 1878 and 1893. For the first 50 years the mechanism of the Baeyer–Villiger reaction was a matter of debate. A side product, 1,2,4,5‐tetraoxocyclohexane, was ruled out as an intermediate in the ester formation by Dilthey. Criegee postulated a nucleophilic attack of the oxidant on the carbonyl group. This mechanism was confirmed by von E. Doering by a labeling experiment with [18O]benzophenone. The rearrangement step occurs with retention of the stereochemistry at the migrating center. The competitive migration and the rate‐determining step are also discussed in this review.

show abstract

“…[9] In order to provide a simple and convenient catalytic system for synthetic chemists, we designed an E. coli-based overexpression system for CHMO [10,11] as a second-generation recombinant version of the previously reported "designer yeasts". [12][13][14] By performing whole-cell fermentations, all required cofactors, especially NADPH, are recycled by the organism and it is not necessary to use artificial regeneration systems. [15] In addition the laborious process of enzyme isolation, which is complicated by protein stability, especially in the case of CHMO, can be avoided by wholecell fermentations.…”

Section: Introductionmentioning

confidence: 99%

Microbial Baeyer–Villiger Oxidation of Prochiral Polysubstituted Cyclohexanones by Recombinant Whole‐Cells Expressing Two Bacterial Monooxygenases

Mihovilovic¹,

Rudroff²,

Grötzl³

et al. 2005

Eur J Org Chem

View full text Add to dashboard Cite

The microbial Baeyer-Villiger oxidation of prochiral 3,5-dimethylcyclohexanones bearing various functionalities with recombinant E. coli cells overexpressing cyclohexanone monooxygenase from Acinetobacter sp. NCIMB 9871 and cyclopentanone monooxygenase from Comamonas sp. NCIMB 9872 has been investigated. A distinct difference in substrate specificity and stereoselectivity of the two enzymes was observed, and enantiocomplementary products were obtained in some cases. The biocatalytic systems enabled ac-

show abstract

A “Designer Yeast” That Catalyzes the Kinetic Resolutions of 2-Alkyl-Substituted Cyclohexanones by Enantioselective Baeyer−Villiger Oxidations

Cited by 84 publications

References 23 publications

Cloning and Characterization of a Gene Cluster Involved in Cyclopentanol Metabolism in Comamonas sp. Strain NCIMB 9872 and Biotransformations Effected by Escherichia coli -Expressed Cyclopentanone 1,2-Monooxygenase

Cloning and Characterization of a Gene Cluster Involved in Cyclopentanol Metabolism in Comamonas sp. Strain NCIMB 9872 and Biotransformations Effected by Escherichia coli -Expressed Cyclopentanone 1,2-Monooxygenase

100 Years of Baeyer–Villiger Oxidations

Microbial Baeyer–Villiger Oxidation of Prochiral Polysubstituted Cyclohexanones by Recombinant Whole‐Cells Expressing Two Bacterial Monooxygenases

Contact Info

Product

Resources

About