The dispiroketones 46 have been synthesized and rearranged by treatment with acids yielding the bicyclic enone 36 under kinetic control and the [3.3.3]propellane 37 under thermodynamic control. The corresponding alcohols 10-12 all yield the [3.3.3]propeUane 41. The rearrangement of [7,7-D2)-12 to [8
Towards a synthesis of (±)modhephene via cascade rearrangement: Synthesis and rearrangement of dispiro[3.0.4.2]undecanes to [3.3.3]propellanes
✍ Scribed by Lutz Fitjer; Marita Majewski; Andreas Kanschik
- Publisher
- Elsevier Science
- Year
- 1988
- Tongue
- French
- Weight
- 147 KB
- Volume
- 29
- Category
- Article
- ISSN
- 0040-4039
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📜 SIMILAR VOLUMES
## Abstract Treatment of (+)‐sclareolide (**1**) with polyphosphoric acid or __Eaton'__s reagent furnished, besides the anticipated cyclopentenone (−)‐**12** and its isomer (−)‐**15**, two diastereoisomeric [4.3.3]propellanes (−)‐**13** and (−)‐**14**, which possess interesting woody‐ambery odors.
## Abstract Formation of (−)‐[4.3.3]propellane 4 from (−)‐14‐hydroxymodhephene (2) proceeds through a Wagner‐Meerwein rearrangement via C3C4 bond‐shift to give a stable intermediate, dimethylcyclohexadienyl cation A, which undergoes deprotonation. Herein, this mechanism was investigated by using a