Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 56, Issue 3, Pages 897-901Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201608206
Keywords
alkaloids; asymmetric synthesis; Kornblum oxidation; Pauson-Khand reaction; sigmatropic rearrangement
Categories
Funding
- Deutsche Forschungsgemeinschaft [SFB 749]
- Center for Integrated Protein Science Munich (CIPSM)
- Verband der Chemischen Industrie
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Sinoracutine is a recently isolated alkaloid with unusual stereochemical and biological properties. It features an unprecedented tetracyclic 6/6/5/5 skeleton that bears an N-methylpyrrolidine ring fused to a cyclopentenone. Interestingly, both enantiomers of sinoracutine have been independently isolated from the same plant, yet the molecule does not appear to occur as a racemate. Here, we present a short synthesis of (-)-sinoracutine that relies on a highly diastereo-selective Pauson-Khand reaction and a Mandai-Claisen reaction to install the quaternary stereocenter. Our work establishes the absolute configuration of the levorotatory isomer and suggests that the optical purity of sinoracutine varies in nature due to its gradual racemization. Experimental evidence supports this proposal, and a plausible mechanism for the racemization is provided.
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