Synthesis of the Sporolide Ring Framework through a Cascade Sequence Involving an Intramolecular [4+2] Cycloaddition Reaction of ano-Quinone

Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA.
Angewandte Chemie International Edition (Impact Factor: 11.26). 02/2008; 47(8):1432-5. DOI: 10.1002/anie.200705334
Source: PubMed


Eine Reaktionssequenz, die eine neuartige intramolekulare [4+2]-Cycloaddition einschließt, lieferte ausgehend vom o-Chinoninden-Intermediat 1, das aus einem Catecholsubstrat hergestellt worden war, den Makrocyclus 2. Die Sequenz war der Schlüssel zum Aufbau der heptacyclischen Struktur 3 der marinen Naturstoffe Sporolid A und B, die aus den Fermentationsbrühen der betreffenden Actinomyceten isoliert wurden.

Download full-text


Available from: Yefeng Tang, Mar 01, 2015
  • Source
    • "Examples of this compound class occur naturally, for example, as pigments in bacteria, fungi, and certain higher plants. Substrates for their endogenous synthesis include malonyl coenzyme A (Schirispsema et al., 1999) or shikimic and mevalonic acid (Nakanishi, 1975). These substrates, in turn, become sources of quinones when consumed by some animals. "
    [Show abstract] [Hide abstract]
    ABSTRACT: In this paper, we present a brief review of quinoid systems, focusing on their chemical synthesis over the last decade. We address not only major methods of synthesizing quinoids, but also their involvement in biological processes. We highlight their medical relevance and versatility, including antitumor, antiretroviral, or antihypertensive agents, properties determined by their various patterns of substitution. Graphical Abstract: [Figure not available: see fulltext.]
    Medicinal Chemistry Research 10/2015; 24(10). DOI:10.1007/s00044-015-1412-y · 1.40 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Electrochemical synthesis of o-benzoquinone derivatives and their in situ transformation are one of the versatile approaches for the synthesis of derivatized catechols. In the present work, electrochemical oxidation of catechols 1a–1d in the presence of a unique nucleophile, 4-amino-3-methyl-5-mercapto-1,2,4-triazole 3, bearing two nucleophilic groups (–NH2 and –SH), have been studied in phosphate buffer solutions using cyclic voltammetry and controlled-potential electrolysis (CPE) methods. The results show that only the mercapto group participated selectively in the Michael addition reaction and led to the formation of catechol substituted products of types 4 and 5, bearing a free amino group, potentially useful for further chemical modifications, e.g. of interest in biomedical applications. Various electrolytic conditions, such as the nature of anode material, amount of passed charge, pH of the electrolytic solution and cell configuration (divided or undivided cell), were also investigated to optimize the yields of corresponding products.
    Journal of electroanalytical chemistry 01/2009; 625(2):131-137. DOI:10.1016/j.jelechem.2008.10.019 · 2.73 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: An ocean of discovery: The first total synthesis of the highly oxygenated, marine-derived, natural product sporolide B has been achieved through a convergent strategy. The key steps involve a ruthenium-catalyzed [2+2+2] cycloaddition to assemble the indene structural motif and a thermally induced Diels-Alder-type reaction to forge the macrocycle (see scheme).
    Angewandte Chemie International Edition 04/2009; 48(19):3449-53. DOI:10.1002/anie.200900264 · 11.26 Impact Factor
Show more