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Issue 43, 2012
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Inter- and intramolecular reactions of 1-deoxy-1-thio-1,6-anhydrosugars with α-diazoesters: synthesis of the tagetitoxin core by photochemical ylide rearrangement

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Abstract

The one-carbon ring expansion of 1-deoxy-1-thio-1,6-anhydrosugars, mediated by metal carbenes and proceeding through the intermediacy of sulfur ylides, has been proposed as a route for the synthesis of the tagetitoxin skeleton. Intermolecular reactions of such thioanhydrosugars with diazoesters afford a range of undesired products derived from the initially formed ylide, whereas use of an intramolecular process generates stable ylides which can be converted to the tagetitoxin skeleton by photo-Stevens rearrangement. Computational studies using density functional theory indicate that the photochemical rearrangement likely proceeds through a homolysis-recombination pathway.

Graphical abstract: Inter- and intramolecular reactions of 1-deoxy-1-thio-1,6-anhydrosugars with α-diazoesters: synthesis of the tagetitoxin core by photochemical ylide rearrangement

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Publication details

The article was received on 09 Jul 2012, accepted on 30 Aug 2012 and first published on 31 Aug 2012


Article type: Paper
DOI: 10.1039/C2OB26308D
Citation: Org. Biomol. Chem., 2012,10, 8616-8627
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    Inter- and intramolecular reactions of 1-deoxy-1-thio-1,6-anhydrosugars with α-diazoesters: synthesis of the tagetitoxin core by photochemical ylide rearrangement

    A. J. Price Mortimer, J. R. H. Plet, O. A. Obasanjo, N. Kaltsoyannis and M. J. Porter, Org. Biomol. Chem., 2012, 10, 8616
    DOI: 10.1039/C2OB26308D

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