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Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition–rearrangement
journal contribution
posted on 2023-06-08, 21:08 authored by David M Hodgson, Carolina Villalonga-Barber, Jonathan M Goodman, Silvina C PellegrinetReaction of diazodiketoesters 17 and 28 with methyl glyoxylate in the presence of catalytic rhodium(II) acetate generates predominantly the 6,8-dioxabicyclo[3.2.1]octanes 29 and 30, respectively. Acid-catalysed rearrangement of the corresponding alcohol 31 favours, at equilibrium, the 2,8-dioxabicyclo[3.2.1]octane skeleton 33 of the squalestatins–zaragozic acids. Force field calculations on the position of the equilibrium gave misleading results. DFT calculations were correct in suggesting that the energy difference between 31 and 33 should be small, but did not always suggest the right major product. Calculation of the NMR spectra of the similar structures could be used to assign the isomers with a high level of confidence.
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- Published
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- Published version
Journal
Organic and Biomolecular ChemistryISSN
1477-0520Publisher
Royal Society of ChemistryExternal DOI
Issue
17Volume
8Page range
3975-3984Department affiliated with
- Chemistry Publications
Full text available
- Yes
Peer reviewed?
- Yes
Legacy Posted Date
2015-06-16First Open Access (FOA) Date
2015-06-16First Compliant Deposit (FCD) Date
2015-06-16Usage metrics
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