Trichothecene degradation studies. 3. Synthesis of 12,13-deoxy-12,13-methanoanguidine and 12-epianguidine, two optically active analogues of the epoxytrichothecene mycotoxin anguidine

Article abstract of DOI:10.1021/jo00380a022

The title compounds were synthesized in order to further explore the apparent requirement of the trichothecene 12,13-epoxide unit for biological activity. Cyclopropane analogue 4 was prepared via a sequence involving a Simmons-Smith cyclopropanation of the anguidine degradation intermediate 6, whereas the key step in the synthesis of 12-epianguidine (5) was the dimethylsulfonium methylide mediated cyclopropanation of norketone 9. These compounds are among the first skeletally modified, semisynthetic trichothecene analogues to be prepared for biological evaluation.