ChemInform Abstract: Utilization of the Phenylthio Substituent as a Multipurpose Synthetic Tool. Direct Application to the Enantioselective Construction of (-)-Salsolene Oxide.
✍ Scribed by L. A. PAQUETTE; L.-Q. SUN; T. J. N. WATSON; D. FRIEDRICH; B. T. FREEMAN
- Publisher
- John Wiley and Sons
- Year
- 2010
- Weight
- 38 KB
- Volume
- 29
- Category
- Article
- ISSN
- 0931-7597
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✦ Synopsis
Utilization of the Phenylthio Substituent as a Multipurpose Synthetic Tool. Direct Application to the Enantioselective Construction of (-)-Salsolene Oxide.
-A key step in the synthesis of the title compound (XI) is cyclization of the ketene generated from the derivative (II) to the bicyclic ketone (III) which is strongly promoted by the present S-Ph group. The S-Ph group in (III) directs introduction of a vinyl cation in that stereocontrolled fashion which enables oxy-Cope rearrangement yielding the ketone (VII). Interestingly, removal of the S-Ph group in the alcohol (VIII) proceeds with inversion of bridgehead olefin geometry. -(PAQUETTE, L. A.