Studies on the synthesis of enol acetates of the .DELTA.1-3-oxo AB-trans steroid system

Oscar R. Rodig; Galal Zanati

doi:10.1021/jo01280a029

On steroids. XXXVI. Catalytic hydrogenation of steroidal enol acetates; A new synthesis of testosterone and oestradiol

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19601078 ◽

1960 ◽

Vol 25 (4) ◽

pp. 1078-1085 ◽

Cited By ~ 4

Author(s):

J. Fajkoš

Keyword(s):

Catalytic Hydrogenation ◽

New Synthesis ◽

Enol Acetates

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Electrochemical Synthesis of Fluorinated Ketones from Enol Acetates and Sodium Perfluoroalkyl Sulfinates

Organic Letters ◽

10.1021/acs.orglett.1c01643 ◽

2021 ◽

Author(s):

Vera A. Vil’ ◽

Valentina M. Merkulova ◽

Alexey I. Ilovaisky ◽

Stanislav A. Paveliev ◽

Gennady I. Nikishin ◽

...

Keyword(s):

Electrochemical Synthesis ◽

Enol Acetates

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The photoaddition of 1,3-diketonatoboron difluorides with benzene derivatives

Canadian Journal of Chemistry ◽

10.1139/v91-064 ◽

1991 ◽

Vol 69 (3) ◽

pp. 423-431 ◽

Cited By ~ 18

Author(s):

Yuan L. Chow ◽

Xinxin Ouyang

Keyword(s):

Crystallographic Analysis ◽

Secondary Oxidation ◽

Enol Ethers ◽

X Ray ◽

Thermal Reactions ◽

Secondary Reactions ◽

Enol Acetates ◽

Orthogonal Orientation ◽

Acid Catalyzed ◽

Boron Difluoride

The boron difluoride complexes of 2-acetylcyclohexanone, 2-acetylcyclopentanone, and acetylacetone (abbreviated as ACHBF2, ACPBF2, and AABF2) were irradiated in the presence of benzene to give the 1:1 adducts as the primary photoadducts; for certain BF2 complexes, toluene, chlorobenzene, benzonitrile, and methyl benzoate were also used as substrates. The 1,5-diketone photoadducts were assumed to form by a [2+2] photocycloaddition followed by cyclobutane opening and hydrolysis to give 1,2 adducts. They undergo a variety of secondary thermal reactions, probably acid catalyzed, to give enol ethers, enol acetates, acetophenones, and ketonylacetophenones. The efficiency of these secondary reactions determines the final products. Photoaddition with a monosubstituted benzene preferentially occurs at the 3,4 bond without regioselectivity. Under oxygen, ACHBF2 photolytically reacts with benzene to give a secondary oxidation product of a 10-membered cyclic alkylphe-none, which is proven by X-ray crystallographic analysis to have the benzene ring and carbonyl group in orthogonal orientation. It is shown that the singlet excited state ACHBF2 initiates the photoaddition, probably through the formation of the benzene exciplex, which could be detected by its emission. While the Stern–Volmer rates are small, the quantum yield of photoaddition products is as high as 0.12–0.19 under limiting conditions. Key words: [2+2] photocycloaddition, non-planar alkanophenone, macrocyclic alkanophenone, boron difluoride complexes, photoaddition to benzenes.

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Production of 16β-(acetoxy)acetoxy derivatives by reaction of 17-keto steroid enol acetates with lead (IV) acetate

Steroids ◽

10.1016/s0039-128x(01)00103-9 ◽

2001 ◽

Vol 66 (10) ◽

pp. 743-748 ◽

Cited By ~ 7

Author(s):

M Numazawa

Keyword(s):

Enol Acetates

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Catalyst‐Free and Oxidant‐Free Cascade Difluoroalkylation and Controllable C−F Bond Activation of Aryl Enol Acetates for the Synthesis of β‐Fluoroenones and β‐Enaminones

Advanced Synthesis & Catalysis ◽

10.1002/adsc.202100681 ◽

2021 ◽

Author(s):

Wenshuang Li ◽

Ruyan Liu ◽

Ruonan Li ◽

Shihaozhi Wang ◽

Dianjun Li ◽

...

Keyword(s):

Bond Activation ◽

Catalyst Free ◽

Enol Acetates

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Microbial hydroxylation of steroids. 6. Hydroxylation of C-6-substituted androst-4-ene-3,17-diones by Rhizopusarrhizus ATCC 11145

Canadian Journal of Chemistry ◽

10.1139/v79-257 ◽

1979 ◽

Vol 57 (13) ◽

pp. 1585-1587 ◽

Cited By ~ 4

Author(s):

Herbert L. Holland ◽

Peter R. P. Diakow

Keyword(s):

Microbial Hydroxylation ◽

Enol Acetates

The products arising from the incubations of C-6α and C-6β chloro-, fluoro-, and methyl-substituted Δ4-3-keto steroids with the C-6β hydroxylating fungus Rhizopusarrhizus ATCC 11145 have been identified, and their formation rationalised in terms of Δ3,5 enolic intermediates. The incubations of C-6 chloro and methyl Δ3,5 enol acetates with R. arrhizus, and the oxidations by m-chloroperoxybenzoic acid of the corresponding enol ethyl ethers have also been described. The relevance of the results so obtained to the mechanism of C-6β hydroxylation of Δ4-3-keto steroids by R. arrhizus is discussed.

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