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Concise Total Syntheses Of Dipiperidine Alkaloids Virgidivarine And Virgiboidine Through Ru‐Mediated Ene‐Ene‐Yne Ring Rearrangement Metathesis (RRM)

S. Kress, J. Weckesser, S. Schulz, S. Blechert
Published 2013 · Chemistry

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Herein, we report on the first enantioselective synthesis of the sparteine-type alkaloids virgidivarine (1) and virgiboidine (2). The stereoselective construction of the challenging dipiperidine core within 1 and 2 was realized by applying an intramolecular ene-ene-yne ring-rearrangement metathesis (RRM) protocol. In combination with this sequence, an unprecedented tandem metathesis/oxidation reaction was established. Subsequent to the RRM event, the Ru-alkylidene species was converted into the highly potent dihydroxylation catalyst RuO4 by the addition of NaIO4. This transformation rendered five sequential reactions that include an ene-ene-yne RRM/dihydroxylation/glycol cleavage in a one-pot procedure. This approach provides practical and general access to dipiperidines and piperidino-quinolizidines. Despite their wide use in organic and organometallic chemistry as well as their occurrence in biologically active natural products, methods are still lacking for the stereoselective synthesis of these motifs.
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