A counterintuitive stereochemical outcome from a chelation-controlled vinylmetal aldehyde addition leads to the configurational reassignment of phormidolide A.
Accepted version
Peer-reviewed
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Repository DOI
Change log
Authors
Lam, Nelson YS https://orcid.org/0000-0002-9307-0619
Muir, Garrett
Challa, Venugopal Rao
Britton, Robert https://orcid.org/0000-0002-9335-0047
Paterson, Ian https://orcid.org/0000-0002-8861-9136
Abstract
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).
Description
Keywords
0305 Organic Chemistry
Journal Title
Chem Commun (Camb)
Conference Name
Journal ISSN
1359-7345
1364-548X
1364-548X
Volume Title
55
Publisher
Royal Society of Chemistry (RSC)
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All rights reserved