Total synthesis of spirotenuipesines A and B Journal Article

   


Authors: Dai, M.; Krauss, I. J.; Danishefsky, S. J.
Article Title: Total synthesis of spirotenuipesines A and B
Abstract: (Chemical Equation Presented) Spirotenuipesines A and B, isolated from the entomopathogenic fungus Paecilomyces tenuipes by Oshima and co-workers, have been synthesized. The synthesis features the highly stereoselective construction of two vicinal all-carbon quaternary centers (C5 and C6) via an intramolecular cyclopropanation/radical initiated fragmentation sequence and a diastereoselective intermolecular Diels-Alder reaction between α-methylenelactone dienophile 20 and synergistic diene 6a. Installation of the C9 tertiary alcohol occurred via nucleophilic methylation. An RCM reaction to produce a tetrasubstituted double bond in the presence of free allylic alcohol and homoallylic oxygenated functional group is also described. This route shortened the synthesis of 11 from 9 steps to 3 steps. We have further developed a strategy to gain access to optically active spirotenuipesines A and B through the synthesis of enantioenriched 10 from commercially available R-(-)-epichlorohydrin. © 2008 American Chemical Society.
Keywords: cyclopropanes; magnetic resonance spectroscopy; models, molecular; crystallography, x-ray; chemical reactions; heterocyclic compounds; chemical equations; molecular conformation; synthesis (chemical); stereoisomerism; spiro compounds; indicators and reagents; functional groups; free radicals; diastereoselective; chemical bonds; allylic alcohols; diels-alder reactions; dienophile; double bonds; entomopathogenic funguses; epichlorohydrin; gain accesses; optically actives; oxygenated functional groups; paecilomyces; rcm reactions; stereoselective constructions; synthesis features; synthesis of; tertiary alcohols; total syntheses
Journal Title: Journal of Organic Chemistry
Volume: 73
Issue: 24
ISSN: 0022-3263
Publisher: American Chemical Society  
Date Published: 2008-12-19
Start Page: 9576
End Page: 9583
Language: English
DOI: 10.1021/jo8016814
PUBMED: 18973385
PROVIDER: scopus
PMCID: PMC2646666
DOI/URL:

http://www.scopus.com/inward/record.url?eid=2-s2.0-58049206907&partnerID=40&md5=6cd567dfbebaba65946c4073ce2e0e14
Notes: --- - "Cited By (since 1996): 5" - "Export Date: 17 November 2011" - "CODEN: JOCEA" - "Source: Scopus"
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MSK Authors
  1. Isaac Krauss
    6 Krauss
  2. Samuel J Danishefsky
    539 Danishefsky
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