Graduate Thesis Or Dissertation
 

Synthetic transformations of shikimic acid

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  • Four strategies which involve synthetic elaboration of the shikimate nucleus are discussed. Methyl shikimate was differentially protected as the 3,4-0-cyclopentylidene ketal and as the 5- 0- tert- butyldiphenylsilyl ether. The methyl ester was then reduced with diisobutylaluminum hydride and the resulting allylic alcohol was oxidized to aldehyde 47 with pyridinium chlorochromate. The cyclopentylidene protecting group of 47 was removed to liberate the 3-and 4- hydroxyl groups which were acylated with maleic anhydride and succinic anhydride. The acylated aldehydes, as well as aldehyde 47, were converted to their respective dimethylhydrazones. The protected shikimaldehyde 43 was treated with the anion of enamine 61. This resulted in the formation of γ-lactone 63 by initial reaction of the enamine at the aldehyde carbon followed by intramolecular attack of the intermediate alkoxide on the fumarate ester. The shikimate ester 54 and aldehyde 48 were selectively oxidized at the allylic position with manganese dioxide, producing 74 and 75 respectively. Ketoaldehyde 75 was reacted in a Lewis acid catalyzed Diels-Alder reaction with 3,5-dimethylfuran to give 77. Alcohol 46 was converted to vinyl ether 81 which was used in a Claisen rearrangement to extend the shikimate framework at the C-2 position. Subsequent a-methylenation of the resulting pair of diastereomeric aldehydes 82 and 83, followed by intramolecular conjugate addition of a hydroxyl group to the unsaturated aldehyde system, led to acetals 86 and 87.
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