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
| Identifer | oai:union.ndltd.org:UBC/oai:circle.library.ubc.ca:2429/20898 |
| Date | January 1978 |
| Creators | Rickards, Gordon E. |
| Source Sets | University of British Columbia |
| Language | English |
| Detected Language | English |
| Type | Text, Thesis/Dissertation |
| Rights | For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use. |
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