A Configurational Switch Based on Iridium-Catalyzed Allylic Cyclization: Application in Asymmetric Total Syntheses of Prosopis, Dendrobate, and Spruce Alkaloids
✍ Scribed by Christian Gnamm; Kerstin Brödner; Caroline M. Krauter; Günter Helmchen
- Publisher
- John Wiley and Sons
- Year
- 2009
- Tongue
- English
- Weight
- 575 KB
- Volume
- 15
- Category
- Article
- ISSN
- 0947-6539
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✦ Synopsis
Abstract
A method for the stereoselective synthesis of 2,6‐disubstituted piperidines has been developed that is based on the use of an intramolecular iridium‐catalyzed allylic substitution as a configurational switch. The procedure allows the preparation of 2‐vinylpiperidines with enantiomeric excesses (ee) of greater than 99 %. As applications, total syntheses of piperidine alkaloids have been elaborated, most often by using Ru‐catalyzed cross‐metatheses as a key step for introduction of a side chain. Asymmetric total syntheses of the prosopis alkaloids (+)‐prosopinine, (+)‐prosophylline, (+)‐prosopine, and of the dendrobate alkaloid (+)‐241D and its C6 epimer are described.