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Syntheses of (±)-α- and (±)- γ- Lycorane via a Stereocontrolled Organopalladium Route
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry, Organic Chemistry.
1991 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 56, no 9, p. 2988-2993Article in journal (Refereed) Published
Abstract [en]

Total syntheses of (+/-)-alpha-and (+/-)-gamma-lycorane are described. The key steps in the syntheses are the stereocontrolled palladium-catalyzed intramolecular 1,4-chloroamidation of 12 to 13 and the subsequent anti-stereoselective copper-catalyzed S(N)2' reaction of allylic chloride 13 with [3,4-(methylenedioxy)phenyl]magnesium bromide to give 14. Hexahydroindole 14 has the required relative stereochemistry between carbons 3a, 7, and 7a for alpha-lycorane (1a) and was transformed to the latter via 15 and 16. The epimeric gamma-lycorane (2) was obtained by performing the Bischler-Napieralski cyclization on 14, which led to a highly stereoselective isomerization to give exclusively 17. Compound 17 was subsequently transformed to 2. The overall yield from ester 8 to (+/-)-alpha- and (+/-)-gamma-lycorane was 40 and 36%, respectively.

Place, publisher, year, edition, pages
1991. Vol. 56, no 9, p. 2988-2993
National Category
Organic Chemistry
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URN: urn:nbn:se:uu:diva-84527DOI: 10.1021/jo00009a011ISI: A1991FJ84000011OAI: oai:DiVA.org:uu-84527DiVA, id: diva2:112435
Available from: 2006-11-16 Created: 2006-11-16 Last updated: 2017-12-14Bibliographically approved

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Andersson, PherGogoll, Adolf

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