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  Total Syntheses of Ipomoeassin B and E

Fürstner, A., & Nagano, T. (2007). Total Syntheses of Ipomoeassin B and E. Journal of the American Chemical Society, 129(7), 1906-1907. doi:10.1021/ja068901g.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-000F-91A3-F Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0028-18E4-F
Genre: Journal Article

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[226]SI.pdf (Supplementary material), 5MB
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 Creators:
Fürstner, Alois1, Author              
Nagano, Takashi1, Author              
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1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              

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 Abstract: A concise, flexible, and efficient total synthesis of the cytotoxic resin glycosides ipomoeassin B (1) and ipomoeassin E (2) is reported which features the advantages of a novel protecting group strategy employing (Z)-3-dimethyl(phenyl)silyl-2-propenoic acid as cinnamic acid surrogate. The use of this readily available compound allowed the macrocycle of the glycolipids to be formed by ring closing olefin metathesis (RCM) with the aid of the second generation Grubbs carbene complex 12. The resulting E/Z mixture could be selectively hydrogenated using Wilkinson's catalyst [RhCl(PPh<sub>3</sub>)sub>3</sub>] without affecting the unsaturated esters in the periphery of the compound, before the C-silyl group was cleaved off with TASF [tris(dimethylamino)sulfonium difluorotrimethylsilicate] under notably mild conditions to release the required cinnamate moiety. Other key steps of the synthesis route comprise the formation of the disaccharide linkage by the trichloroacetimidate method, the formation of the chiral acid segment 19 via a VO(acac)2-catalyzed, tert-BuOOH-induced oxidative rearrangement of the optically pure furyl alcohol (−)-15 (Achmatowicz-type reaction), and a reductive cleavage of the 4,6-O-p-methoxybenzylidene acetal in 5 with NaBHsub>3</sub>CN and Mesub>3</sub>SiCl (TMSCl), the regiochemical course of which was found to be opposite to that previously reported in the literature for sterically less encumbered substrates.

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Language(s): eng - English
 Dates: 2006-12-132007-01-252007-02-21
 Publication Status: Published in print
 Pages: 2
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: eDoc: 337722
DOI: 10.1021/ja068901g
ISI: 000244206400035
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Title: Journal of the American Chemical Society
  Other : J. Am. Chem. Soc.
  Abbreviation : JACS
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 129 (7) Sequence Number: - Start / End Page: 1906 - 1907 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870