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Aromatics to triquinanes: p-cresol to (+/-)-Delta(9(12))-capnellene

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Title Aromatics to triquinanes: p-cresol to (+/-)-Delta(9(12))-capnellene
 
Creator SINGH, V
PRATHAP, S
PORINCHU, M
 
Subject asymmetric total synthesis
sesquiterpene (+/-)-ceratopicanol
beta,gamma-unsaturated ketone
natural-products
squarate esters
(+/-)-delta-9(12)-capnellene
rearrangement
cyclization
methane
(-)-delta(9(12))-capnellene
 
Description A novel, efficient and stereospecific synthesis of the marine natural product capnellene from p-cresol is described. Generation of 4-methyl-6,6-spiroepoxycyclohexa-2,4-die (9) from 5-methylsalicyl alcohol (8), its in situ cycloaddition with cyclopentadiene (in situ), and the photochemical oxa-di-pi-methane reaction of an endo tricyclo[5.2.2.O-2,O-6]undecenone are the key features of our strategy. An efficient synthetic route to appropriately designed endo tricyclo[5.2.2.0(2,6)]undecenones (compounds 6, 11-13) endowed with most of the structural and stereochemical features of capnellene, from the keto epoxide 7, are described. The photochemical reaction of 6, and 11b,d upon sensitized irradiation readily gave the oxa-di-pi-methane products 5, 14, and 15 respectively. The tetracyclic compound 5 was elaborated to capnellene after cleavage of the peripheral cyclopropane bond, Barton's deoxygenation, deprotection of the carbonyl group, and Wittig reaction.
 
Publisher AMER CHEMICAL SOC
 
Date 2011-07-13T17:22:58Z
2011-12-26T12:47:59Z
2011-12-27T05:42:56Z
2011-07-13T17:22:58Z
2011-12-26T12:47:59Z
2011-12-27T05:42:56Z
1998
 
Type Article
 
Identifier JOURNAL OF ORGANIC CHEMISTRY, 63(12), 4011-4017
0022-3263
http://dx.doi.org/10.1021/jo980064g
http://dspace.library.iitb.ac.in/xmlui/handle/10054/3727
http://hdl.handle.net/10054/3727
 
Language en