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Reactive species from aromatics and oxa-di-π-methane rearrangement: a stereoselective synthesis of (±)-hirsutene from salicyl alcohol

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Title Reactive species from aromatics and oxa-di-π-methane rearrangement: a stereoselective synthesis of (±)-hirsutene from salicyl alcohol
 
Creator SINGH, VISHWAKARMA
VEDANTHAM, PUNITHA
SAHU, PRAMOD K
 
Subject oxidation
cycloaddition
synthesis
 
Description A total synthesis of hirsutene, a triquinane sesquiterpene, from salicyl alcohol is reported. Oxidation of salicyl alcohol in the presence of cyclopentadiene gave 9-spiroepoxy-endo-tricyclo[5.2.2.02,6]undeca-4,10-dien-8-one which was elaborated to the 3-hydroxy-2-methyl-endo-tricyclo[5.2.2.02,6]undeca-10-en-8-one containing major structural and functional features of hirsutene. Photochemical sigmatropic 1,2-acyl shift in 3-hydroxy-2-methyl-endo-tricyclo[5.2.2.02,6]undeca-10-en-8-one followed by radical induced cleavage of peripheral cyclopropane bond, olefination and Simmon–Smith reaction furnished 11-hydroxy-1-methyl-4-spirocyclopropanetricyclo[6.3.0.02,6]undecane that upon treatment with hydrogen on PtO2 and PCC oxidation gave 1,4,4-trimethyltricyclo[6.3.0.02,6]undecan-11-one, a known precursor. Wittig methylenation on this precursor gave hirsutene.
 
Publisher Elsevier
 
Date 2009-02-20T07:29:06Z
2011-11-25T17:37:01Z
2011-12-26T13:06:16Z
2011-12-27T05:54:05Z
2009-02-20T07:29:06Z
2011-11-25T17:37:01Z
2011-12-26T13:06:16Z
2011-12-27T05:54:05Z
2004
 
Type Article
 
Identifier Tetrahedron 60(37), 8161-8169
0040-4020
http://dx.doi.org/10.1016/j.tet.2004.06.096
http://hdl.handle.net/10054/720
http://dspace.library.iitb.ac.in/xmlui/handle/10054/720
 
Language en