Clark, J.S. , Berger, R., Hayes, S.T., Senn, H.M. , Farrugia, L.J., Thomas, L.H., Morrison, A.J. and Gobbi, L. (2013) Total syntheses of multiple cladiellin natural products by use of a completely general strategy. Journal of Organic Chemistry, 78(2), pp. 673-696. (doi: 10.1021/jo302542h)
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Abstract
The enantioselective total syntheses of 10 cladiellin natural products have been completed, starting from the known allylic alcohol (+)-14, which can be prepared in large quantities. The bridged tricyclic core of the cladiellins has been constructed via three ring-forming reactions: (i) an intramolecular reductive cyclization between an aldehyde and an unsaturated ester, mediated by samarium(II) iodide, to form a tetrahydropyranol; (ii) reaction of a metal carbenoid, generated from a diazo ketone, with an ether to produce an ylide-like intermediate that rearranges to produce E- or Z-oxabicyclo[6.2.1]-5-undecen-9-one; and (iii) a Diels–Alder cycloaddition reaction to construct the third ring found in the core structure of the cladiellins. The key ring-forming reaction, in which a diazo ketone is converted into a bridged bicyclic ether, can be tuned to give either of the isomeric oxabicyclo[6.2.1]-5-undecen-9-ones as the major product by switching from a copper to a rhodium catalyst and selecting the appropriate reaction conditions. The tricyclic products obtained from the three-step sequence involving the Diels–Alder cycloaddition reaction can be employed as advanced intermediates to prepare a wide range of cladiellin natural products.
Item Type: | Articles |
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Status: | Published |
Refereed: | Yes |
Glasgow Author(s) Enlighten ID: | Clark, Professor Stephen and Farrugia, Dr Louis and Berger, Miss Raphaelle and Senn, Dr Hans and Thomas, Dr Lynne |
Authors: | Clark, J.S., Berger, R., Hayes, S.T., Senn, H.M., Farrugia, L.J., Thomas, L.H., Morrison, A.J., and Gobbi, L. |
College/School: | College of Science and Engineering > School of Chemistry |
Journal Name: | Journal of Organic Chemistry |
ISSN: | 0022-3263 |
Published Online: | 06 December 2012 |
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