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Total Syntheses of Multiple Cladiellin Natural Products by Use of a Completely General Strategy

Total Syntheses of Multiple Cladiellin Natural Products by Use of a Completely General Strategy

J Stephen Clark, Raphaëlle Berger, Stewart T Hayes, Hans Martin Senn, Louis J Farrugia, Lynne H Thomas, Angus J Morrison, Luca Gobbi

J Org Chem. 2013 Jan 18;78(2):673-96.

PMID: 23215006

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.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP13813257	Samarium(III) iodide		13813-25-7	Price

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