A synthesis-enabled relative configurational assignment of the C31-C46 region of hemicalide.
Chem Commun (Camb)
Royal Society of Chemistry (RSC)
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Stockdale, T. P., Lam, N., & Paterson, I. (2022). A synthesis-enabled relative configurational assignment of the C31-C46 region of hemicalide.. Chem Commun (Camb) https://doi.org/10.1039/d2cc01802k
With 21 unknown stereocentres embedded in spatially separated stereoclusters, the cytotoxic polyketide hemicalide represents a seemingly intractible structural assignment problem. Herein, through the targeted synthesis of configurationally defined fragments, as well as "encoded" mixtures of diastereomers, the stereochemical elucidation of the C31-C46 region of hemicalide is achieved. Detailed NMR spectroscopic analysis of candidate fragments and comparison with the related hemicalide data strongly supported a 31,32-syn, 32,36-anti and 42,46-anti relationship. In combination with previous work on hemicalide, this reduces the number of possible structural permutations down to a more manageable eight diastereomers.
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External DOI: https://doi.org/10.1039/d2cc01802k
This record's URL: https://www.repository.cam.ac.uk/handle/1810/336122
Attribution 4.0 International
Licence URL: https://creativecommons.org/licenses/by/4.0/