The total synthesis of isocomene has been accomplished in seventeen steps. Robinson annelation of 2-methylcyclopentanone with 1,4-dimethoxy-2-butanone gave 1,2,3,6,7,7a-hexahydro-4-methoxy-7a-methyl-5H-indene-5-one. Lithium aluminum hydride reduction of the latter followed by a Simmons-Smith cyclopropanation reaction with ethylidene diiodide and diethyl zinc resulted in the formation of an (alpha)-oxycyclopropylcarbinol. This was elaborated by conventional methods into the crucial intermediate, 2(alpha),4,5,7(beta)-tetramethyl-3(alpha)-methoxy-4-hydroxytricyclo{5.3.0.0('1,3)}dec-5-ene, whose cyclopropylcarbinyl rearrangement product was a cyclobutanone. Ring enlargement of the latter formed 3-oxoisocomene, from which isocomene was obtained readily.
| Identifer | oai:union.ndltd.org:RICE/oai:scholarship.rice.edu:1911/15664 |
| Date | January 1982 |
| Creators | ARRHENIUS, THOMAS SVANTE |
| Source Sets | Rice University |
| Language | English |
| Detected Language | English |
| Type | Thesis, Text |
| Format | application/pdf |
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