The acid-catalyzed cyclizations of various aromatic diazoacetamides were studied and general and efficient preparations of isoquinolinones, benzazepinones, and spirodienone lactams were realized. The scope and limitations of these cyclization reactions were investigated. / In the presence of anhydrous trifluoroacetic acid, $\alpha$-unsubstituted $N$-methyldiazoacetamides were cyclized to give isoquinolinones in 60-80% yield. Cyclization of the diazoacetamides under these conditions, except with immediate addition of water, afforded spirodienone lactams in similar yields. Formation of the spirocycles under the rapid aqueous quench conditions demonstrated the intermediacy of spirodienone oxonium ions formed via preferential exo-trig cyclization. The cyclizations of other $\alpha$-unsubstituted $N$-methyldiazoacetamides were found to proceed similarly to afford isoquinolinones, benzazepinones, and spirodienone lactams. A limitation to this method was encountered when $\alpha$-substituted $N$-methyldiazoacetamides were found to cyclize to spirodienone lactams in only 10-20% yield. The inefficient cyclization of $\alpha$-substituted diazoacetamides was attributed to a conformational effect. To overcome this effect, $\alpha$-substituted $N$-tert-butyldiazoacetamides were prepared and were efficiently cyclized to 1-substituted isoquinolinones in 60-80% yield. / Spirodienone lactams prepared by this method were demonstrated to be synthetically useful. Rearrangement of these compounds in the presence of boron trifluoride etherate in refluxing nitromethane proceeded regiospecifically to afford phenolic isoquinolinones in 80-90% yield. / The described reactions were employed in synthetic approaches to the alkaloids morphine and colchicine. / Source: Dissertation Abstracts International, Volume: 50-03, Section: B, page: 0969. / Major Professor: Martin A. Schwartz. / Thesis (Ph.D.)--The Florida State University, 1989.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_77989 |
| Contributors | Rishton, Gilbert Michael., Florida State University |
| Source Sets | Florida State University |
| Language | English |
| Detected Language | English |
| Type | Text |
| Format | 132 p. |
| Rights | On campus use only. |
| Relation | Dissertation Abstracts International |
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