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  Total Synthesis of (S)-(+)-Citreofuran by Ring Closing Alkyne Metathesis

Fürstner, A., Castanet, A.-S., Radkowski, K., & Lehmann, C. W. (2003). Total Synthesis of (S)-(+)-Citreofuran by Ring Closing Alkyne Metathesis. The Journal of Organic Chemistry, 68(4), 1521-1528. doi:10.1021/jo026686q.

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 Creators:
Fürstner, Alois1, Author              
Castanet, Anne-Sophie1, Author              
Radkowski, Karin1, Author              
Lehmann, Christian W.2, Author              
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1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              
2Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445625              

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 Abstract: A concise total synthesis of citreofuran 4 is described, a structurally unique octaketide derivative belonging to the curvularin family. Key steps involve the elaboration of orsellinic acid methyl ester 5 to acid 14, which converts, on attempted formation of the corresponding acid chloride, to the 3-alkoxyisocoumarin derivative 20. This heterocycle can be used as an activated ester to give ketone 21 on treatment with 3- pentynylmagnesium bromide in the presence of TMSCl as the activating agent. Ring- closing alkyne metathesis (RCAM) of diyne 21 catalyzed by (tBuO)<sub>3</sub>W≡CCMe<sdub>3</sub> affords the strained cycloalkyne 22. Treatment with acid renders its triple bond susceptible to nucleophilic attack by the adjacent carbonyl group, thus leading to a transannular cycloaromatization with formation of the intact skeleton of citreofuran. An X-ray crystallographic study reveals conformational. details about this natural product. Finally, it is shown that 4 as well as its protected precursor 23 are able to cleave double-stranded DNA under oxidative conditions.

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Language(s): eng - English
 Dates: 2002-11-112003-01-232003-02-21
 Publication Status: Published in print
 Pages: 8
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jo026686q
 Degree: -

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Title: The Journal of Organic Chemistry
  Other : J. Org. Chem.
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: - Volume / Issue: 68 (4) Sequence Number: - Start / End Page: 1521 - 1528 Identifier: ISSN: 0022-3263
CoNE: https://pure.mpg.de/cone/journals/resource/954925416967_1