Issue 38, 2022

A synthesis-enabled relative configurational assignment of the C31–C46 region of hemicalide

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.

Graphical abstract: A synthesis-enabled relative configurational assignment of the C31–C46 region of hemicalide

Supplementary files

Article information

Article type
Communication
Submitted
29 Mar 2022
Accepted
14 Apr 2022
First published
14 Apr 2022
This article is Open Access
Creative Commons BY license

Chem. Commun., 2022,58, 5729-5732

A synthesis-enabled relative configurational assignment of the C31–C46 region of hemicalide

T. P. Stockdale, N. Y. S. Lam and I. Paterson, Chem. Commun., 2022, 58, 5729 DOI: 10.1039/D2CC01802K

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