Total syntheses of (+)- and (-)-peribysin E Journal Article

   


Authors: Angeles, A. R.; Waters, S. P.; Danishefsky, S. J.
Article Title: Total syntheses of (+)- and (-)-peribysin E
Abstract: A convergent, stereocontrolled route to either antipode of the cell adhesion inhibitor, peribysin E, has been achieved from carvone. Highlights of the synthesis include a Diels-Alder reaction to generate a cis-decalin framework, followed by semipinacol-type ring contraction to secure the stereochemistry of the C7 quaternary center. Potential mechanistic pathways for the critical ring contraction were studied through deuterium incorporation studies. In addition, an optimized olefin isomerization/Saegusa oxidation protocol is described for the conversion of [4+2] cycloadducts of 2-(trialkylsilyloxy)-1,3-dienes to 1,6(2H,7H)-naphthalenediones, having stereochemical arrangements not accessible via conventional Robinson annulation protocols. Finally, the ability to independently prepare either enantiomer of peribysin E from the corresponding antipode of carvone led to a reassignment of the absolute configuration of peribysin E. © 2008 American Chemical Society.
Keywords: unclassified drug; molecular structure; chemical reactions; cell adhesion; oxidation; diels-alder reaction; diels alder reaction; synthesis; synthesis (chemical); stereochemistry; iodine; alkadiene; isomerization; adhesion; cross-linking reagents; ethers; annulation reaction; naphthalene derivative; indans; carvone; decalin; ring-contraction; 1,6(2h,7h)naphthalenedione; alkene; peribysin e; isomerism; naphthalenes
Journal Title: Journal of the American Chemical Society
Volume: 130
Issue: 41
ISSN: 0002-7863
Publisher: American Chemical Society  
Date Published: 2008-09-01
Start Page: 13765
End Page: 13770
Language: English
DOI: 10.1021/ja8048207
PUBMED: 18783227
PROVIDER: scopus
PMCID: PMC2646880
DOI/URL:

http://www.scopus.com/inward/record.url?eid=2-s2.0-53849102606&partnerID=40&md5=e647b78a89b126fceb61f803b51dea0e
Notes: --- - "Cited By (since 1996): 8" - "Export Date: 17 November 2011" - "CODEN: JACSA" - "Source: Scopus"
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MSK Authors
  1. Angie R Angeles
    4 Angeles
  2. Stephen Paul Waters
    2 Waters
  3. Samuel J Danishefsky
    539 Danishefsky
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