The enantioselective approach to bonandiol, also known as magydardiendiol, has utilized two novel synthetic methodologies. The first is the diastereoselective cyclopropanation of a homochiral eneketal prepared from (2R,3R)- or (2S,3S)-2,3-butanediol and possessing C₂ symmetry. Simmons-Smith cyclopropanation gave good diastereoselectivity (69-75%) in addition to excellent amounts of monocyclopropanated material obtained (90-96%). The second method utilized is the nickel acetylacetonate catalyzed coupling of dimethylzinc to a sterically hindered cyclic β-keto enolphosphate in 76-92% yield. This approach to the A ring of hyperforin starting from commercially available citral allows for the introduction of all but one isoprenyl appendage.
| Identifer | oai:union.ndltd.org:arizona.edu/oai:arizona.openrepository.com:10150/184428 |
| Date | January 1988 |
| Creators | Heidt, Philip Conrad. |
| Contributors | Mash, Eugene, Bates, Robert, Hruby, Victor, Rund, John, Law, John |
| Publisher | The University of Arizona. |
| Source Sets | University of Arizona |
| Language | English |
| Detected Language | English |
| Type | text, Dissertation-Reproduction (electronic) |
| Rights | Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. |
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