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Molecular complexity from aromatics. Cycloaddition of spiroepoxycyclohexa-2,4-dienones and intramolecular Diels-Alder reaction: a stereoselective entry into tetracyclic core of atisane diterpenoids

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Title Molecular complexity from aromatics. Cycloaddition of spiroepoxycyclohexa-2,4-dienones and intramolecular Diels-Alder reaction: a stereoselective entry into tetracyclic core of atisane diterpenoids
 
Creator SINGH, V
BHALERAO, P
SAHU, BC
MOBIN, SM
 
Subject Oxidative dearomatization
Cyclohexa-2,4-dienones
pi(4)s+pi(2)s cycloaddition
Atisane diterpenoids
Intramolecular Diels-Alder reaction
HOMOALLYL RADICAL REARRANGEMENT
NATURAL-PRODUCT SYNTHESIS
SYNTHETIC APPROACH
ORGANIC-SYNTHESIS
(+/-)-METHYL GUMMIFEROLATE
OXIDATIVE DEAROMATIZATION
PHENOL DEAROMATIZATION
SYSTEMS
ROUTE
ACID
 
Description A stereoselective approach to tetracyclic core of atisane diterpenoids is described. Oxidative dearomatization, intermolecular cycloaddition of spiroepoxycyclohexa-2,4-dieone with ethyl acrylate, and intramolecular inverse demand pi(4)s+pi(2)s cycloaddition are the key features of our design. Oxidation of appropriately appended o-hydroxymethyl phenols to corresponding 6,6-spiroepoxycyclohexadienones followed by cycloaddition with ethyl acrylate furnished bridged bicyclo[2.2.2]octanes disposed with appropriate functionality. Regioselective manipulation of functional groups led to highly embellished bicyclic systems endowed with appendages containing diene and dienophilic moieties that upon inverse electron demand intramolecular cycloaddition provide the tetracyclic framework of atisanes in stereoselective fashion. A remarkable effect of a remote functional group on intramolecular Diels-Alder reaction has also been described. (C) 2012 Elsevier Ltd. All rights reserved.
 
Publisher PERGAMON-ELSEVIER SCIENCE LTD
 
Date 2014-10-14T17:49:48Z
2014-10-14T17:49:48Z
2013
 
Type Article
 
Identifier TETRAHEDRON, 69(1)137-146
http://dx.doi.org/10.1016/j.tet.2012.10.051
http://dspace.library.iitb.ac.in/jspui/handle/100/14610
 
Language en