The total synthesis of mitomycins via isomitomycin A is described. Key reactions are a Michael-type coupling reaction between chalcone (94)* and 5-ethylthio-2-trimethylsiloxyfuran, followed by an azido-olefin cyclization. The first route took 30 steps from 2,6-dimethoxytoluene in a overall yield of 6%. The improved second route contains 26 steps with overall yield of 10% from the same staring material. Resolution of an synthetic intermediate resulted in both (+)- and ($-$)-isomitomycin A (15). X-ray crystallographic analysis of an intermediate with known chiral auxiliary which led to the natural ($-$)-isomitomycin A unequivocally determined the absolute stereochemistry of mitomycins. ftn*Please refer to dissertation for diagrams.
| Identifer | oai:union.ndltd.org:RICE/oai:scholarship.rice.edu:1911/16409 |
| Date | January 1990 |
| Creators | Yang, Lihu |
| Contributors | Fukuyama, T. |
| Source Sets | Rice University |
| Language | English |
| Detected Language | English |
| Type | Thesis, Text |
| Format | 230 p., application/pdf |
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