Darstellung und Eigenschaften monohalogenierter 3‐Keto‐Δ<sup>4.6</sup>‐dien‐steroide

Brückner, Klaus; Hampel, Bruno; Johnsen, U.

doi:10.1002/cber.19610940510

Cited by 37 publications

(4 citation statements)

References 18 publications

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“…Three of the four oxygen atoms of virone were present as 1 700 cm-'; 6, 209.1) is located in a COMe group (6,(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18), suggesting a pregnan-20-one skeleton.…”

Section: IImentioning

confidence: 99%

Viridin. Part 8. Structures of the analogues virone and wortmannolone

Blight¹,

Grove²

1986

J. Chem. Soc., Perkin Trans. 1

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The secondary metabolic products virone (from Gliocladium virens) and wortmannolone (from Penicillium wortmannii) are shown to be pregna-5,8-dieno[6,5,4-bc]furan-3,7,20-trione and 1 a,2aepoxy-3P-hydroxyandrosta-5,8-dieno[6,5,4-bc]furan-7,17-dione, respectively.Viridin (1; R ' = OH, R2 = OMe, R3R4 = 0),2 a steroidal secondary metabolite of the fungus Gliocludium uirens Miller,3 CMI 24039 (a fungus erroneously described in the early work 4*5' as Trichodermu uiride), has conventionally been produced in surface culture on Raulin Thom medium at 25 "C. When this fermentation is carried out at 32 "C, viridin is obtained in much reduced yield (5-10 mg/l as opposed to 25 mg/l) but is accompanied (2 mg/l) by a less polar metabolite of composition C22H2404 to which we have assigned the trivial name virone. Virone is not produced at all at 25 "C.The related steroidal metabolite wortmannin (2) ' *' is produced by some strains of Penicilfium wortmannii Klocker,* but not by all. With one strain (CMI 44277), wortmannin is accompanied by a metabolite (trivial name, wortmannolone) of composition CtOH2005. This paper is concerned with the chemistry and structural elucidation of virone (3) and wortmannolone ( 4 R'R2 = 0, R3 = OH, R4 = H).In common with viridin and its analogues,' wortmannolone and its derivatives tenaciously retained solvent of crystallisation and solvent-free material could not always be obtained for analysis. Wortmannolone (4; R'R2 = 0, R3 = OH, R4 = H) contained two carbonyl groups (vmx. 1 71 5 and 1 665 cm-') and a secondary hydroxy group (vmaX. 3 360 an-') which was readily acetylated to give acetylwortmannolone (4; R'R2 = 0, R3 = OAc, R4 = H) (vmaX. OH absent; 6,6.16), and readily oxidised by the chromic oxide-sulphuric acid reagent to a dehydro * Because of the biosynthetic implications of this work, triterpenoid rather than viridin numbering' is used. 21GOMe 0 -CH -CH-CHOR-

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Section: IImentioning

confidence: 99%

Viridin. Part 8. Structures of the analogues virone and wortmannolone

Blight¹,

Grove²

1986

J. Chem. Soc., Perkin Trans. 1

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“…[170][171] (2 H, s, 21-H2), 3.65 (1 H, br s, w+ 8 Hz, 7-H), 1.71 (3 H, 4 2 Hz, 2-H), 5 . 0 -6P,7a-Diazido-9a-jluoro-l6a-methyl-3,20-dioxopvegna-1,4diene-1 1 p, 1 7a,2 1 -trio1 2 1 -Acetate ( 14). *-In a manner similar to that described above, reaction of 9~x-fluoro-16a-methyl-3,20-dioxopregna-l,4,6-triene-l lp,l7a,21-triol 21-acetate (12) (432 mg, 1 mmol) with lead tetra-acetate (886 mg, 2 mmol) and trimethylsilyl azide (1.06 ml, 8 mmol) gave, after column chromatography on silica gel, 6p,7 a-diazid0-9a-fluoro-16amethyl-3,20-dioxopregna-l ,4-diene-1 lp,l7a,21-triol 21-acetate (14) (100 rng, 19%), crystallised from ether (52 mg), m.p.…”

mentioning

confidence: 99%

Synthesis of steroidal azides. Part 2. Reaction of 4,6-dien-3-ones with lead tetra-acetate and trimethylsilyl azide

Draper¹

1983

J. Chem. Soc., Perkin Trans. 1

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“…The only chloro-substituted Cii-progestational steroid to have been widely used is chlormadinone acetate (II) (Ringold et al, 1959;Brückner et al, 1961). Its metabolism in women has been investigated (Bermudez et al, 1968), but the identity of its metabolites has not been reported.…”

mentioning

confidence: 99%