A Bioinspired Synthesis of (±)-Rubrobramide, (±)-Flavipucine, and (±)-Isoflavipucine.

@article{Mizutani2016ABS,
  title={A Bioinspired Synthesis of (±)-Rubrobramide, (±)-Flavipucine, and (±)-Isoflavipucine.},
  author={Shoma Mizutani and Kenta Komori and Tohru Taniguchi and Kenji Monde and Kouji Kuramochi and Kazunori Tsubaki},
  journal={Angewandte Chemie},
  year={2016},
  volume={55 33},
  pages={
          9553-6
        }
}
A biomimetic synthesis of naturally occurring lactams rubrobramide, flavipucine, and isoflavipucine is described. The key step is a regioselective Darzens reaction between isobutyl glyoxal and an α-bromo-β-ketoamide. The construction of the core tricyclic ring system of rubrobramide was achieved by a cascade reaction in a single step from an α,β-epoxy-γ-lactam. Furthermore, the absolute configuration of naturally occurring (+)-rubrobramide was determined by vibrational circular dichroism… Expand
19 Citations
Polyketides and a Dihydroquinolone Alkaloid from a Marine-Derived Strain of the Fungus Metarhizium marquandii.
TLDR
Three new natural products, including two butenolide derivatives and one dihydroquinolone derivative, together with nine known natural products were isolated from a marine-derived strain of the fungus Metarhizium marquandii, suggesting that the fungus produces aflaquinolone I with a different configuration (chiral switching). Expand
Antiproliferative Activity of the Cyclization Products of 1-(2-Oxocyclohexyl)Ethane-1,1,2,2-Tetracarbonitrile and α,β-Unsaturated Aldehydes
The antiproliferative activity of previously obtained 3-R-6-imino-2,7-dioxabicyclo[3.2.1.]octane-4,4,5-tricarbonitriles was tested on 59 cell lines obtained from human lung, colon, brain, ovary,Expand
α-Halogenoacetamides: versatile and efficient tools for the synthesis of complex aza-heterocycles.
TLDR
This review provides an overview of the applications of α-halogenoacetamides in domino and cycloaddition reactions and modulation of the reactivity of these compounds opens the way to a large panel of reactions and therefore to aLarge diversity of aza-heterocycles. Expand
The second generation synthesis of (±)-berkeleyamide D
Abstract Previously, our group reported the first synthesis of (±)-berkeleyamide D, optical resolution of both enantiomers, and determination of their absolute configuration. The synthesis providedExpand
Synthesis, antibacterial and cytotoxic evaluation of flavipucine and its derivatives.
TLDR
Results indicate that the pyridione epoxide moiety is a pharmacophore for antibacterial activity against B. subtilis and flavipucine showed cytotoxic activity against several cancer cells. Expand
The reaction of prop-2-ynylsulfonium salts and sulfonyl-protected β-amino ketones to epoxide-fused 2-methylenepyrrolidines and S-containing pyrroles.
A novel divergent domino annulation reaction of prop-2-ynylsulfonium salts with sulfonyl-protected β-amino ketones has been developed, affording various epoxide-fused 2-methylenepyrrolidines andExpand
Bicyclic acetals: biological relevance, scaffold analysis, and applications in diversity-oriented synthesis.
TLDR
A summary of some recent efforts on the development of acetal-containing small molecule collections through DOS approaches is reported, highlighting the great potential of bicyclic acetals in Diversity-Oriented Synthesis (DOS). Expand
Metal-free regioselective direct thiolation of 2-pyridones.
TLDR
A combination of persulfate and a commercially available halide source enables the successful direct incorporation of a sulfide moiety into the 5-position of pyridone under mild conditions, providing a useful and convenient approach for the preparation of a diverse array of 5-thio-substituted p Pyridones in moderate to excellent yields. Expand
Silver(I)-Catalyzed Enantioselective [3+2]-Cycloaddition Reaction of α-Silylimines: A Facile Route to Quaternary-Carbon-Rich Scaffolds.
A silver-catalyzed highly enantioselective 1,3-dipolar cycloaddition reaction of α-silylimines with pyrone-based trisubstituted olefins was developed affording bi- and tricyclicExpand
Safety of the fungal workhorses of industrial biotechnology: update on the mycotoxin and secondary metabolite potential of Aspergillus niger, Aspergillus oryzae, and Trichoderma reesei
TLDR
This review presents an update on the current knowledge of the secondary metabolite potential of the major fungal species used in industrial biotechnology, i.e., Aspergillus niger, As pergillus oryzae, and Trichoderma reesei, and a description of all known secondary metabolites produced by these species. Expand
...
1
2
...

References

SHOWING 1-10 OF 17 REFERENCES
(+)‐Flavipucine, the Missing Member of the Pyridione Epoxide Family of Fungal Antibiotics
From the culture extracts of the endophytic fungus, Phoma sp., isolated from the plant Salsola oppositifolia, five secondary metabolites were isolated and characterized. On biomalt agar medium, theExpand
Flavipucine (3'-isovaleryl-6-methylpyridine-3-spiro-2'-oxiran-2(1H),-4(3H)-dione), an antibiotic from Aspergillus flavipes.
  • J. Findlay, L. Radics
  • Chemistry, Medicine
  • Journal of the Chemical Society. Perkin transactions 1
  • 1972
The structures of three metabolites produced by a strain of Aspergillus flavipes are discussed including a previously described antibiotic, which is shown to beExpand
Rubrobramide, a cytotoxic and phytotoxic metabolite from Cladobotyrum rubrobrunnescens.
TLDR
Cladobotrin (1) and rubrobramide (2), possessing a unique oxidized tricyclic system, is a new compound structurally related to flavipucine (3), which also is produced by the fungus. Expand
The X-ray crystal structure of (±)-flavipucine
Synthetic (±)-flavipucine (C12H15O4N) is monoclinic, space groupP21/c, with a = 11.506(5), b = 8.765(5), c = 11.981(7) A, β = 91.09(2)°, Z = 4. X-ray analysis confirms its structure as 1,Expand
Short synthesis of berkeleyamide D and determination of the absolute configuration by the vibrational circular dichroism exciton chirality method.
TLDR
The first synthesis of (±)-berkeleyamide D has been accomplished and the absolute configurations of both enantiomers of ber Berkeleyamide D were determined by the vibrational circular dichroism exciton chirality method. Expand
Synthesis and biological activity of flavipucine analogues.
TLDR
A series of analogues of flavipucine prepared possessing side chain as well as nuclear variants were found to exhibit enhanced activity against several bacteria and fungi as compared with the natural product itself. Expand
Flavipucine and Brunnescin, Two Antibiotics from Cultures of the Mycophilic Fungus Cladobotryum rubrobrunnescens
TLDR
The metabolite isolated from submerged cultures of Cladobotryum rubrobrunnescens, a mycophilic fungus growing on a Inocybe species, is a new tetrasubstituted furan derivative which exhibits antibacterial, antifungal and cytotoxic effects. Expand
Stereochemical analysis of glycerophospholipids by vibrational circular dichroism.
TLDR
Through the first systematic application of vibrational circular dichroism (VCD) spectroscopy to various diacylated GPLs, it is revealed that their chirality can be assigned by the sign of a VCD exciton couplet generated by the interaction of two carbonyl groups. Expand
Notiz zur Darstellung von 4-Hydroxy-6-methyl-5,6-dihydro-2H-pyran-2-on
Meldrum's acid (2) is acylated by diketen affording the acylMeldrum's acid3. In aqueous bicarbonate its 3-oxogroup is selectively reduced by sodium tetrahydroborate giving the alcohol4, which readilyExpand
Multifactorial induction of an orphan PKS-NRPS gene cluster in Aspergillus terreus.
TLDR
Gene inactivation and stable isotope labeling experiments unveiled the molecular basis for flavipucine/fruit rot toxin biosynthesis. Expand
...
1
2
...