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- Title
Photochemical High-yield Preparation of Tricyclo [3.3.0.0<sup>2,8</sup>]octan-3-ones. Potential Synthons for Polycyclopentanoid Terpenes and Prostacyclin Analogs. Preliminary Communication.
- Authors
Demuth, Martin; Raghavan, Palaykotai R.; Carter, Charles; Nakano, Koichi; Schaffner, Kurt
- Abstract
Three-step syntheses and the resolution into the enantiomers are reported for the tricyclo[3.3.0.02,8]octan-3-ones 7-9, which are destined to serve as synthons for polycyclopentanoid terpenes and prostacyclin analogs. Routine overall yields of ca. 75% for 7, 40% for 8, and 46% for 9 are obtained, with 2-chloroacrylonitrile and 1,3-cyclohexadiene (for 7) and 1-methyl-1,4-cyclohexadiene (for 8 and 9) as the starting materials. The key step is the triplet-sensitized oxadi-π-methane photorearrangement of the β,γ-unsaturated ketones 1-3 which can be achieved in 80-90% yields of isolated product and quantum yields of 0.5-1.0. The racemates of both ketone 1 and its photoisomer 7 have been resolved via chromatographic separation of suitable diastereoisomeric acetal mixtures. On the other hand, sensitization of 1 with an optically active donor, (-)- 14, gave only an impractical maximum enantiomeric excess of 10% (-)- 7.
- Publication
Helvetica Chimica Acta, 1980, Vol 63, Issue 8, p2434
- ISSN
0018-019X
- Publication type
Article
- DOI
10.1002/hlca.19800630836