1412898-41-9Relevant academic research and scientific papers
Inter- and intramolecular reactions of 1-deoxy-1-thio-1,6-anhydrosugars with α-diazoesters: Synthesis of the tagetitoxin core by photochemical ylide rearrangement
Price Mortimer, Anne J.,Plet, Julien R. H.,Obasanjo, Oluwafunsho A.,Kaltsoyannis, Nikolas,Porter, Michael J.
, p. 8616 - 8627 (2013/01/15)
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.
