Total synthesis of the potent anticancer Aglaia metabolites (-)-silvestrol and (-)-episilvestrol and the active analogue (-)-4'-desmethoxyepisilvestrol.

@article{Adams2009TotalSO,
  title={Total synthesis of the potent anticancer Aglaia metabolites (-)-silvestrol and (-)-episilvestrol and the active analogue (-)-4'-desmethoxyepisilvestrol.},
  author={Tim E. Adams and Mariana El Sous and Bill C. Hawkins and Sebastian Hirner and Georgina A. Holloway and Mui Ling Khoo and David J. Owen and G Paul Savage and Peter J. Scammells and Mark A. Rizzacasa},
  journal={Journal of the American Chemical Society},
  year={2009},
  volume={131 4},
  pages={
          1607-16
        }
}
Total synthesis of the anticancer 1,4-dioxane containing natural products silvestrol (1) and episilvestrol (2) is described by an approach based on the proposed biosynthesis of these novel compounds. The key steps included an oxidative rearrangement of the protected d-glucose derivative 11 to afford the 1,4-dioxane 12, which could be elaborated to the coupling partner 5 and a photochemical [3 + 2]-cycloadditon between the 3-hydroxyflavone 27 and methyl cinnamate followed by base-induced alpha… Expand
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Silvestrol and episilvestrol, potential anticancer rocaglate derivatives from Aglaia silvestris.
Two cytotoxic rocaglate derivatives possessing an unusual dioxanyloxy unit, silvestrol (1) and episilvestrol (2), were isolated from the fruits and twigs of Aglaia silvestris by bioassay-guidedExpand
1-O-Alkylation of D-Glucopyranose
Abstract Direct 1-O-methylation of 1-O-metalated 2,3,4,6-tetra-O-benzyl-d-glucose (1) with methyl trifluoromethanesulfonate (3a) as a strong alkylating agent led to the methyl gluco-pyranosides 4aExpand
A Practical Synthesis of Mannosaminyl-β(1→4)-glucosyl-α(1→2)-rhamnose, the Trisaccharide Repeating Unit of a Streptococcus pneumoniae Capsular Polysaccharide
An efficient chemical synthesis is described for the title trisaccharide repeating unit of the capsular polysaccharide of Streptococcus pneumoniae Type 19F. The key intermediate was a well-accessibleExpand
Synthesis of the novel anti-leukaemic tetrahydrocyclopenta[b]benzofuran, rocaglamide and related synthetic studies
Two approaches to the rocaglamide tricyclic skeleton are described. The first, which employs an unusual intramolecular dithianyl anion to carbonyl addition reaction, provides access to α-phenylExpand
Stereoselective synthesis of (+/-)-rocaglaol analogues.
TLDR
An intramolecular hydroxy epoxide opening was used to access the cyclopenta[b]benzofuran ring system of the natural product rocaglaol and this strategy is well-suited for the production of analogues with variation of the western ring. Expand
Epoxidation of alkenes by dioxirane intermediates generated in the reaction of potassium caroate with ketones
Kinetics and 180-labeling experiments have provided evidence for the involvment of dioxirane intermediates 2a (Scheme I) in the ketone-catalyzed decomposition of potassium peroxomonosulfate (KHS05,Expand
Total synthesis of (±)-rocaglamide and some aryl analogues
Abstract The insecticidal activity found for rocaglamide and its congeners, prompted us to establish a short and efficient synthesis of the natural product and some synthetic ‘halo-aryl’ analogues.Expand
A new analogue of rocaglamide by an oxidative dihydrofuran synthesis
Abstract A new analogue of rocaglamide 1 has been synthesised. The tricyclic core structure that is lacking the C-8b hydroxy group was generated in an oxidative addition of 1,3-cyclohexanedione to aExpand
Stereospecific synthesis of (+/-)-1,2-anhydro methyl rocaglate.
TLDR
This letter shows that 14 is converted into 5 as a single stereoisomer and subsequently transformed into 1,2-anhydro methyl rocaglate 20. Expand
STRUCTURE AND REACTIONS OF GLYCOPYRANOSIDE DERIVED DIALDEHYDES
Several 4- protected D-glucopyranosides were synthesized and cleaved by sodium metaperiodate. Depending on the protection pattern the resulting dialdehydes showed different types of structures.Expand
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