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Novel Concise Synthesis of (−)‐Clausenamide
Author(s) -
Liu Di,
Yu Xiaoming,
Huang Liang
Publication year - 2013
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.201201187
Subject(s) - chemistry , aminolysis , stereoselectivity , stereospecificity , yield (engineering) , substrate (aquarium) , lactone , amide , stereochemistry , alcohol , organic chemistry , catalysis , materials science , oceanography , metallurgy , geology
A six‐step synthesis of (−)‐clausenamide is described. Optically pure ( R , E )‐1,3‐diphenylallylic alcohol was acetylated and then subjected to an Ireland‐Claisen rearrangement, giving the γ , δ ‐unsaturated acid, which underwent a substrate‐induced stereoselective bromolactonization to afford the expected all‐equatorial substituted bromo‐ δ ‐lactone. An unusual chemo‐selective aminolysis of the lactone resulted in the formation of a γ , δ ‐epoxy‐amide in stereospecific manner. Base‐promoted cyclization of this intermediate and the subsequent Davis oxidation furnished the synthesis, delivering the final product in >99% ee and up to 34% overall yield.