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Issue 17, 2010
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Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloadditionrearrangement

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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.

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

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Publication details

The article was received on 19 Mar 2010, accepted on 08 Jun 2010 and first published on 02 Jul 2010


Article type: Paper
DOI: 10.1039/C004496B
Citation: Org. Biomol. Chem., 2010,8, 3975-3984
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    Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloadditionrearrangement

    D. M. Hodgson, C. Villalonga-Barber, J. M. Goodman and S. C. Pellegrinet, Org. Biomol. Chem., 2010, 8, 3975
    DOI: 10.1039/C004496B

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