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Asymmetric total syntheses of tuberostemonine, didehydrotuberostemonine, and 13-epituberostemonine

Wipf, P and Spencer, SR (2005) Asymmetric total syntheses of tuberostemonine, didehydrotuberostemonine, and 13-epituberostemonine. Journal of the American Chemical Society, 127 (1). 225 - 235. ISSN 0002-7863

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Detailed experimental approaches toward the pentacyclic Stemona alkaloids tuberostemonine and didehydrotuberostemonine and the close analogue 13-epituberostemonine are described. The syntheses originate with a hydroindolinone derivative that can be obtained on a large scale in a single step from carbobenzoxy-protected L-tyrosine. Highlights of the conversion of this hydroindolinone to the target structures are the three-fold use of ruthenium catalysts, first in azepine ring-closing metathesis and then in alkene isomerization and cross-metathesis propenyl-vinyl exchange, as well as the stereoselective attachment of a γ-butyrolactone ring to a tetracycle core structure by use of a lithiated asymmetric bicyclo-[3.2.1]octane (ABO) ortho ester. Structural analysis by density functional theory (DFT) methods revealed that the ease of oxidation of the natural product is likely due to the conformational preferences of the pyrrolidine and the fused cyclohexane rings.


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Item Type: Article
Status: Published
CreatorsEmailPitt UsernameORCID
Wipf, Ppwipf@pitt.eduPWIPF
Spencer, SR
Date: 12 January 2005
Date Type: Publication
Journal or Publication Title: Journal of the American Chemical Society
Volume: 127
Number: 1
Page Range: 225 - 235
DOI or Unique Handle: 10.1021/ja044280k
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 0002-7863
MeSH Headings: Alkaloids--chemical synthesis; Indoles--chemical synthesis; Lactones--chemical synthesis; Models, Molecular; Pyrrolidines--chemical synthesis; Stemonaceae--chemistry
PubMed ID: 15631472
Date Deposited: 30 Jan 2014 17:34
Last Modified: 02 Feb 2019 15:57


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