The structure of 8,11,15-trihydroxy-9,12-oxyeicosa-5,13-dienoic acid A, isolated by Pace-Asciak and Wolfe from enzymatic incubation of arachidonic acid, was proven by the synthesis of 8R,9S,11R,12S,15(R and S) isomers 1a and 1b. Both epimers were more polar than the natural product A. Reductive ozonolysis of 1a, followed by reaction of the resulting 2-acetoxyheptanal with l-ephedrine, gave oxazolidines whose R(,f) values on tlc were found to be characteristic of the chirality of the acetoxy group, thus permitting the determination of the absolute stereochemsitry at C-15 of 1a. / Model studies towards the synthesis of 9,11,15-trihydroxy-8,12-oxyeicosa-5,13-dienoic acid B were carried out.

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Thesis (M.S.)--University of Michigan, 1976. / Typescript (photocopy). Includes bibliographical references (leaves 65-72). Also issued in print.

Thesis (M.S.)--University of Michigan, 1976. / Typescript (photocopy). eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 65-72).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1981. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

The synthesis of an important intermediate (36) in a total synthesis of the prostaglandins was undertaken. Treatment of the monoanion of the pyrrolidine enamine of methyl acetoacetate with cis-4,5-epoxy-2(E)-decen-1-yl mesylate (42) followed by addition of one equivalent of lithium diisopropylamide and then hydrolysis yielded the desired intermediate 36. This intermediate contains the correct relitive stereochemistry between the C-12 and C-15 carbons which has turned out to be the most difficult problem associated with the synthesis of the prostaglandins. Alkylation with trans-4,5-epoxy-2(E)-decen-1-yl mesylate (67) produced the intermediate with the unnatural stereochemistry. The two mesylates were produced stereospecifically, the first starting from propargyl alcohol. In the process of making these two mesylates, two natural products were synthesized, ethyl 2(E),4(Z)-decadienoate (79), isolated from Bartlett pears, and 2(E),4(Z)-decadien-1-yl isovalerate (41), isolated from the essential oils of Cyprus. / Science, Faculty of / Chemistry, Department of / Graduate

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