Synthesis cyclopropene ketal

ROM-CM Sequence The ROM reaction of a cycloalkene engaged in the subsequent CM reaction with an olefinic partner provides the straightforward procedure for the synthesis of diene products having the isolated double bonds. This sequence is applicable not only to relatively strained cycloalkenes but also to unstrained compounds such as cyclohexene. The ROM-CM sequence of norbor-nene compounds or cyclopropene ketals with various olefins is reported for the preparations of natural products. 

Parrain and coworkers described an efficient cascade involving the ring opening of cyclopropene ketal of type 71 followed by CM with a variety of alkenes in the presence of catalyst [Ru]-I for the synthesis of protected divinyl ketones [42]. This sequence was employed by Kozmin and coworkers for the preparation of the linear center portion of bistramide A, a marine metabolite isolated from Lissodinum bistratum which exhibits potent cytotoxicity against several cell lines [43], as well as... 

Scheme 10.23 Cascade ROM/CM of cyclopropene ketal for the synthesis of routiennocin.

Cycloheptatriene.—Synthesis. Details have been published on the preparation of specifically substituted cycloheptatrienes by the cycloadditon of cyclopropenes to thiophene-1,1-dioxides followed by expulsion of S02. Substituted tropones have been obtained from the furan adducts of bromo-oxyallyl cations e.g. treatment of l,l,3,3-tetrabromo-4-methylpentan-2-one with di-iron nonacarbonyl in the presence of furan gave adduct (141) which was converted into a-thujaplicin (142). Acid hydrolysis of the norbornyl ketal (143) followed by warming to 70 "C gave 7,7-dimethyl-cycloheptatriene. ... 

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