Nickel-Catalyzed Cyclizations of Enoate Equivalents:  Application to the Synthesis of Angular Triquinanes

Unsaturated acyloxazolidinones and α‘-silyloxy enones were found to be effective substrates in nickel-catalyzed organozinc-promoted cyclizations. Both groups served as convenient enoate equivalents, whereas methyl enoates themselves were inefficient substrates. A five-step procedure for the conversi...

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Bibliographic Details
Published in:Journal of organic chemistry 1999-08, Vol.64 (16), p.6060-6065
Main Authors: Seo, Jeongbeob, Fain, Hélène, Blanc, Jean-Baptiste, Montgomery, John
Format: Article
Language:English
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Summary:Unsaturated acyloxazolidinones and α‘-silyloxy enones were found to be effective substrates in nickel-catalyzed organozinc-promoted cyclizations. Both groups served as convenient enoate equivalents, whereas methyl enoates themselves were inefficient substrates. A five-step procedure for the conversion of dimethylcyclopentenone into a highly functionalized angular triquinane was developed utilizing this observation. The key step of the procedure involves a nickel-catalyzed reductive cyclization/Dieckmann condensation sequence involving a cyclic enone tethered to an unsaturated acyloxazolidinone or α‘-silyloxy enone. The method was applied in a formal synthesis of pentalenene, pentalenic acid, and deoxypentalenic acid.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo9908389