A counterintuitive stereochemical outcome from a chelation-controlled vinylmetal aldehyde addition leads to the configurational reassignment of phormidolide A.
Chemical communications (Cambridge, England)
Royal Society of Chemistry
MetadataShow full item record
Lam, N., Muir, G., Challa, V. R., Britton, R., & Paterson, I. (2019). A counterintuitive stereochemical outcome from a chelation-controlled vinylmetal aldehyde addition leads to the configurational reassignment of phormidolide A.. Chemical communications (Cambridge, England), 55 (65), 9717-9720. https://doi.org/10.1039/c9cc05067a
As part of our ongoing studies towards the total synthesis of phormidolide A (1), we explored the chelation-controlled vinylmetal addition of iodide 2 to aldehyde 3 to install the reported 17S configuration. While the stereochemical outcome of this reaction was opposite to that expected, detailed NMR comparisons with the previously reported triacetonide derivative of phormidolide A (18) highlighted that the major adduct was a better match to the natural product. The synthesis of three model acetonides and detailed spectroscopic comparisons to the triacetonide derivative of phormidolide A supports a reassignment of seven of the 11 stereocentres in phormidolide A (1a).
External DOI: https://doi.org/10.1039/c9cc05067a
This record's URL: https://www.repository.cam.ac.uk/handle/1810/294879
All rights reserved