A study of the regioselectivity of oxygen insertion in the Baeyer–Villiger oxidation of bicyclo[2.2.1]heptan-2-ones

1991 ◽  
pp. 1793-1802 ◽  
Author(s):  
Peter Hamley ◽  
Andrew B. Holmes ◽  
David R. Marshall ◽  
John W. M. MacKinnon
Keyword(s):  
Oxygen Insertion ◽  
Villiger Oxidation

Baeyer-Villiger oxidation of Δ4-3-Oxo-steroids and 4,5-Epoxy-3-oxo-steroids. A route to some novel A-nor-steroids

1968 ◽  
Vol 21 (7) ◽  
pp. 1873
Author(s):  
JT Pinhey ◽  
K Schaffner
Keyword(s):  
Boron Trifluoride ◽  
Acidic Conditions ◽  
Oxygen Insertion ◽  
Acid Labile ◽  
Villiger Oxidation

Evidence is presented that the Baeyer-Villiger oxidation of Δ4-3-oxo-steroids yields enol-e-lactones which are further oxidized to β-epoxy-e-lactones. The latter are acid labile and rearrange to 5α-acyl-∂-lactones. The sequence appears to be stereospecific, and no 5β-acyl-∂-lactones could be isolated. Baeyer-Villiger oxidation of 4,5-epoxyoholestan-3-ones results in oxygen insertion between C3 and C4. The epoxy-e-lactones were not isolated, since they rearranged under the acidic conditions to give 5-acyl-4-oxacholestan-3-ones. The 5α-acyl epimers differ from the 5β-compounds, by undergoing an internal Claisen-type condensation to give A-norcholestans with a 2,5-lactone bridge. The photochemical, thermal, and boron trifluoride-catalysed conversion of the enol lactone (IIIa) into a-nor-5β-cholestan-3-one is reported.

ChemInform Abstract: A Study of the Regioselectivity of Oxygen Insertion in the Baeyer- Villiger Oxidation of Bicyclo(2.2.1)heptan-2-ones.

ChemInform ◽  
2010 ◽  
Vol 22 (45) ◽  
pp. no-no
Author(s):  
P. HAMLEY ◽  
A. B. HOLMES ◽  
D. R. MARSHALL ◽  
J. W. M. MACKINNON
Keyword(s):  
Oxygen Insertion ◽  
Villiger Oxidation

scholarly journals Cloning, Expression, Characterization, and Biocatalytic Investigation of the 4-Hydroxyacetophenone Monooxygenase from Pseudomonas putida JD1

2009 ◽  
Vol 75 (10) ◽  
pp. 3106-3114 ◽  
Author(s):  
Jessica Rehdorf ◽  
Christian L. Zimmer ◽  
Uwe T. Bornscheuer
Keyword(s):  
Pseudomonas Putida ◽  
Open Reading Frames ◽  
Gene Encoding ◽  
Open Chain ◽  
Aromatic Ketones ◽  
Heteroaromatic Compounds ◽  
Aliphatic Ketones ◽  
Expression Characterization ◽  
Reading Frames ◽  
Villiger Oxidation

ABSTRACT While the number of available recombinant Baeyer-Villiger monooxygenases (BVMOs) has grown significantly over the last few years, there is still the demand for other BVMOs to expand the biocatalytic diversity. Most BVMOs that have been described are dedicated to convert efficiently cyclohexanone and related cyclic aliphatic ketones. To cover a broader range of substrate types and enantio- and/or regioselectivities, new BVMOs have to be discovered. The gene encoding a BVMO identified in Pseudomonas putida JD1 converting aromatic ketones (HAPMO; 4-hydroxyacetophenone monooxygenase) was amplified from genomic DNA using SiteFinding-PCR, cloned, and functionally expressed in Escherichia coli. Furthermore, four other open reading frames could be identified clustered around this HAPMO. It has been suggested that these proteins, including the HAPMO, might be involved in the degradation of 4-hydroxyacetophenone. Substrate specificity studies revealed that a large variety of other arylaliphatic ketones are also converted via Baeyer-Villiger oxidation into the corresponding esters, with preferences for para-substitutions at the aromatic ring. In addition, oxidation of aldehydes and some heteroaromatic compounds was observed. Cycloketones and open-chain ketones were not or poorly accepted, respectively. It was also found that this enzyme oxidizes aromatic ketones such as 3-phenyl-2-butanone with excellent enantioselectivity (E ≫100).

Chemo-enzymatic Baeyer–Villiger oxidation of cyclopentanone and substituted cyclopentanones

2008 ◽  
Vol 54 (3-4) ◽  
pp. 61-66 ◽  
Author(s):  
María Yolanda Rios ◽  
Enrique Salazar ◽  
Horacio F. Olivo
Keyword(s):  
Villiger Oxidation
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