Total synthesis of (±)-jiadifenin and studies directed to understanding its SAR: Probing mechanistic and stereochemical issues in palladium-mediated allylation of enolate-like structures Journal Article


Authors: Carcache, D. A.; Cho, Y. S.; Hua, Z.; Tian, Y.; Li, Y. M.; Danishefsky, S. J.
Article Title: Total synthesis of (±)-jiadifenin and studies directed to understanding its SAR: Probing mechanistic and stereochemical issues in palladium-mediated allylation of enolate-like structures
Abstract: The total synthesis of jiadifenin has been accomplished. The synthesis allows us to build an SAR profile which suggests that the jiadifenin skeleton may be less desirable from the standpoint of nominating a potential drug than that of its prerearrangement precursor. The key steps of the jiadifenin problem involve the construction of two 1,3-related quaternary carbons. The paper describes how the stereochemistry was managed in this context. The issue was studied in considerable detail at the level of a then new allyl transfer reaction arising from a palladium-mediated transfer process of an allyl carbonate. By use of externally deuterated diallyl carbonate, we could probe, for the first time, the Stereochemical relationship between the inter- and intramolecular versions of this process. The existence of concurrent inter- and intramolecular allylation reactions was demonstrated by deuteration experiments. While in the particular case at hand, we find very little difference in Stereochemical outcome as one partitions between the inter- and intramolecular pathways, the techniques employed are applicable to other systems. © 2006 American Chemical Society.
Keywords: unclassified drug; nonhuman; structure activity relation; alkylation; natural product; structure analysis; chemical reactions; reaction analysis; palladium; synthesis; synthesis (chemical); molecular model; carbonates; stereochemistry; carbon; phytochemistry; allyl carbonate; enolate-like structures; jiadifenin skeleton; palladium-mediated allylation; enolase; jiadifenin; allylation; illicium; illicium jiadifengpi
Journal Title: Journal of the American Chemical Society
Volume: 128
Issue: 3
ISSN: 0002-7863
Publisher: American Chemical Society  
Date Published: 2006-01-25
Start Page: 1016
End Page: 1022
Language: English
DOI: 10.1021/ja056980a
PROVIDER: scopus
PUBMED: 16417394
DOI/URL:
Notes: --- - "Cited By (since 1996): 22" - "Export Date: 4 June 2012" - "CODEN: JACSA" - "Source: Scopus"
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  1. Young Shin Cho
    12 Cho
  2. Zihao Hua
    9 Hua
  3. Yueming Li
    132 Li
  4. Yuan Tian
    16 Tian