Novel and efficient synthesis of bicyclo[2.2.2]octenones and sigmatropic shifts in ground and excited states: Stereoselective route to cis-decalins and diquinane frameworks
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Title |
Novel and efficient synthesis of bicyclo[2.2.2]octenones and sigmatropic shifts in ground and excited states: Stereoselective route to cis-decalins and diquinane frameworks
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Creator |
SINGH, V
IYER, SR MOBIN, SM |
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Subject |
diels-alder reaction
sponge agelas-nakamurai masked o-benzoquinones marine sponge natural-products enantioselective synthesis radical cyclization ring-system photochemistry rearrangement |
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Description |
A new and efficient synthesis of a variety of highly embellished bicyclooctenones having an endo-vinyl moiety and their sigmatropic shifts in ground and excited states leading to a stereoselective route to substituted cis-decalins and diquinane frameworks have been described. Functionalized bicyclo[2.2.2]octenones having an endo-vinyl group and a beta,gamma-enone chromophore were prepared by in situ generation of 6-chloromethyl-6-hydroxycyclohexadienones and cycloaddition with butadiene (also generated in situ) followed by manipulation of the adducts. The presence of contiguous carbonyl, hydroxyl, and chloromethyl groups in adducts led to the introduction of various alkyl groups a to the ketone in a stereoselective fashion. The 3,3-sigmatropic shift in the bridged bicyclic compounds gave the corresponding cis-decalins, whereas the triplet sensitized irradiation led to the formation of diquinanes as a result of a 1,2-acyl shift.
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Publisher |
AMER CHEMICAL SOC
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Date |
2011-07-14T14:05:17Z
2011-12-26T12:48:25Z 2011-12-27T05:37:37Z 2011-07-14T14:05:17Z 2011-12-26T12:48:25Z 2011-12-27T05:37:37Z 2005 |
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Type |
Article
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Identifier |
JOURNAL OF ORGANIC CHEMISTRY, 70(3), 973-981
0022-3263 http://dx.doi.org/10.1021/jo048320e http://dspace.library.iitb.ac.in/xmlui/handle/10054/3976 http://hdl.handle.net/10054/3976 |
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Language |
en
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