1. Biomimetic Total Syntheses of (−)-Leucoridines A and C through the Dimerization of (−)-Dihydrovalparicine
- Author
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Michael J. Zdilla, Steven E. Wheeler, Praveen Kokkonda, Trevor J. Seguin, Rodrigo B. Andrade, Shivaiah Vaddypally, and Keaon R. Brown
- Subjects
Models, Molecular ,Reaction mechanism ,Cycloaddition Reaction ,Chemistry ,Stereochemistry ,Total synthesis ,Stereoisomerism ,Sequence (biology) ,General Chemistry ,General Medicine ,Catalysis ,Cycloaddition ,Article ,Indole Alkaloids ,Magnoliopsida ,Biomimetics ,Biomimetic synthesis ,Dimerization - Abstract
Concise biomimetic syntheses of the Strychnos-Strychnos-type bis-indole alkaloids (-)-leucoridine A (1) and C (2) were accomplished through the biomimetic dimerization of (-)-dihydrovalparicine (3). En route to 3, the known alkaloids (+)-geissoschizoline (8) and (-)-dehydrogeissoschizoline (10) were also prepared. DFT calculations were employed to elucidate the mechanism, which favors a stepwise aza-Michael/spirocyclization sequence over the alternate hetero-Diels-Alder cycloaddition reaction.
- Published
- 2015
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