Studies directed toward the total synthesis of gascardic acid

Brown, William Larry (1984) Studies directed toward the total synthesis of gascardic acid. Masters thesis, Memorial University of Newfoundland.

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Abstract

Various reactions directed toward the total synthesis of gascardic acid have been delineated. Unfortunately trisubstituted cyclopentadienes of type 31a and 31b would not partake in the desired intramolecular Diels-Alder reactions. In contrast, compounds 68 and 73 in which the sidechain substituents differ, cyclized to the requisite tricyclic skeletons. -- A general method for inverting the stereochemistry of vinyl alcohols such as 20 and 37 has been developed. This involved a [2,3] sulfoxide rearrangement and will permit a broader application of the oxy-Cope rearrangement as illustrated by the conversion of 37 to 53 to 54. -- Model studies of a suitable cyclohexane-cycloheptane ring expansion in which the keto-ester functionality is retained were commenced.

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