52645-96-2Relevant academic research and scientific papers
The hydroxylation at C-17 in the biosynthesis of the diterpenoid aphidicolin
Hanson, James R.,Hitchcock, Peter B.,Jarvis, Andrew G.
, p. 1055 - 1059 (1997)
The hydroxylation at C-17 in aphidicolin biosynthesis is inhibited by a 17-thiol. A metabolite hydroxylated at C-17 and retaining the cyclopropane ring was obtained from 3α,18-dihydroxy-15β,16β-methanoaphidicolane whilst aphidicolin itself was obtained from 3α,18-dihydroxyaphidicolane when these substrates were incubated with the fungus, Cephalosporium aphidicola.
Biosynthesis of diterpenoid aphidicolin: Isolation of intermediates from P-450 inhibitor treated mycelia of Phoma betae
Oikawa, Hideaki,Ohashi, Satoshi,Ichihara, Akitami,Sakamura, Sadao
, p. 7541 - 7554 (2007/10/03)
Treatment of Phoma betae with P-450 inhibitors caused accumulation of biosynthetic precursors 2, 3 and 4 of aphidicolin (1). Their structures were elucidated by spectroscopic analysis and they were confirmed by chemical transformations from 1. Isotopicall
THE HYDROXYLATION OF GLOBULOL AND 7-EPIGLOBULOL BY CEPHALOSPORIUM APHIDICOLA
Hanson, James R.,Hitchcock, Peter B.,Manickavasagar, Revathy
, p. 1023 - 1026 (2007/10/02)
Globulol and 7-epiglobulol were shown to be hydroxylated by Cephalosporium aphidicola on one (C-14) of the methyl groups geminal to the cyclopropane ring in 48.5 and 56percent yield, respectively.The significance of this hydroxylation adjacent to a cyclopropane ring is noted. - Key words: Cephalosporium aphidicola; globulol; 7-epiglobulol; sesquiterpenoid; microbiological hydroxylation.
Rearrangements of the C/D Ring System of the Tetracyclic Diterpenoid, Aphidicolin
Hanson, James R.,Hitchcock, Peter B.,Jarvis, Andrew G.,Ratcliffe, Arnold H.
, p. 1773 - 1778 (2007/10/02)
The generation of a C-16 carbocation in the aphidicolane series by the hydrolysis of a 15β,16β- or a 16β,17-epoxide is shown to lead, inter alia, to skeletal rearrangement products arising from the migration of the C(12)-C(13) bond to C-16.
Oxidation of Aphidicolin and Its Conversion into 19-Noraphidicolan-16β-ol
Gordon, John F.,Hanson, James R.,Jarvis, Andrew G.,Ratcliffe, Arnold H.
, p. 3019 - 3022 (2007/10/02)
The preparation of the 3α,18-monoacetonide of aphidicolin and its selective oxidation at C-17, is described.Catalytic oxidation of aphidicolin affords 16β-hydroxy-3-oxo-19-noraphidicolan-17-oic acid.The conversion of this into 19-noraphidicolan-16β-ol and its biotransformation by the fungus, Cephalosporium aphidicola, to a 19-noraphidicolin, is reported.
Aphidicolin Synthetic Studies: A Stereocontrolled End Game
Rizzo, Carmelo J.,Smith, Amos B.
, p. 969 - 979 (2007/10/02)
A highly efficient, stereocontrolled synthesis of (+)-aphidicolin 1 from the well-known degradation product, acetonide 17-nor ketone 2a, has been achieved.Key steps included palladium(0)-catalysed carbonylation of the enol triflate derived from 2a and stereoselective epoxidation of the resultant α,β-unsaturated ester.Hydride reduction then furnished the C(16,17) vicinal diol moiety of 1.Similarly transformed to aphidicolin were the Corey 2,2-dimethylpropylidenedioxy synthetic intermediate 2b and the bis-tert-butyldimethylsilyl ether 2c.The latter further served as synthetic precursor to the naturally occurring derivative (+)-aphidicolin 17-acetate 26.The preparation and biological evaluation of the unnatural 16-methoxycarbonyl congeners 28 and 29 are also discussed.
A New End Game for Aphidicolin
Rizzo, Carmelo J.,Smith, Amos B.
, p. 2793 - 2796 (2007/10/02)
A highly efficient, stereocontrolled synthesis of aphidicolin from its degradation product, 3α,18-isopropylidenedioxy-17-noraphidicolan-16-one, has been achieved.
Studies in Terpenoid Biosynthesis. Part 38. The Role of an 16β,17-Epoxyaphidicolane in the Minor Biosynthetic Pathway Leading to Aphidicolin
Ackland, Mark J.,Gordon, John F.,Hanson, James R.
, p. 2009 - 2012 (2007/10/02)
The hydroxylation of 2H, 17-2H3>aphidicolane-3α,16β,18-triol at C-17 in the biosynthesis of aphidicolin is shown to involve an isotope effect whilst there is no effect in the incorporation of 2H, 17-2H2>aphidicol-16-ene-3α,18-diol suggesting that the transformation of the 16-ene involves epoxidation and hydrolysis rather than hydration and hydroxylation.Feeding experiments suggest that the 16β,17-epoxyaphidicolane-3α,18-diol is involved in this transformation.
Studies in Terpenoid Biosynthesis. Part 35. Biosynthetic Sequences leading to the Diterpenoid Aphidicolin in Cephalosporium aphidicola
Ackland, Mark J.,Gordon, John F.,Hanson, James R.,Yeoh, Boon Leng,Ratcliffe, Arnold H.
, p. 1477 - 1480 (2007/10/02)
-Labelled samples of 18-hydroxyaphidicol-16-ene, 3α,18-dihydroxyaphidicol-16-ene, 16β,17- and 16β,18-dihydroxyaphidicolane, and 3α,16β,18- and 16β,17,18-triyhdroxyaphidicolane have been prepared from aphidicolin and shown to be incorporated into aphidicolin by Cephalosporium aphidicola to the extent of 0.86, 16.4, 3.5, 20.5, 52.6, and 16,9 percent , respectively.These results suggest that although the major pathway of aphidicolin biosynthesis involves the 16β-alcohols , the 16-enes may also utilized whilst a metabolic grid relationship may exist between the variously hydroxylated 16β-alcohols.
