A synthesis-enabled relative configurational assignment of the C31-C46 region of hemicalide.
Accepted version
Peer-reviewed
Repository URI
Repository DOI
Change log
Authors
Stockdale, Tegan P
Lam, Nelson YS https://orcid.org/0000-0002-9307-0619
Paterson, Ian https://orcid.org/0000-0002-8861-9136
Abstract
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.
Description
Keywords
Antineoplastic Agents, Magnetic Resonance Spectroscopy, Polyketides, Stereoisomerism
Journal Title
Chem Commun (Camb)
Conference Name
Journal ISSN
1359-7345
1364-548X
1364-548X
Volume Title
Publisher
Royal Society of Chemistry (RSC)