Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition–rearrangement

Hodgson, David M, Villalonga-Barber, Carolina, Goodman, Jonathan M and Pellegrinet, Silvina C (2010) Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition–rearrangement. Organic and Biomolecular Chemistry, 8 (17). pp. 3975-3984. ISSN 1477-0520

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Abstract

Reaction 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.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Depositing User: Carolina Villalonga-Barber
Date Deposited: 16 Jun 2015 14:10
Last Modified: 25 Mar 2019 16:30
URI: http://sro.sussex.ac.uk/id/eprint/54547

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