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Volumn 6, Issue 21, 2004, Pages 3743-3746

Total synthesis of (-)-α-kainic acid by (-)-sparteine-mediated asymmetric deprotonation-cycloalkylation

Author keywords

[No Author keywords available]

Indexed keywords

CARBAMIC ACID DERIVATIVE; KAINIC ACID DERIVATIVE; PYRROLIDINE DERIVATIVE; SPARTEINE;

EID: 7044241215     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0485666     Document Type: Article
Times cited : (35)

References (40)
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    • note
    • This synthetic route could be also applicable for the synthesis of (-)-domoic acid by modifying precursor A with a dienoic side chain.
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    • 4) unsuccessfully.
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    • Synthesized from hydroxyacetone in 67% overall yield over four steps: silylation followed by Horner - Wadsworth - Emmons reaction, 1,2-reduction of the ester moiety, and bromination.
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    • (-)-MPTA ester 10 was derived from racemic and enantiomerically enriched 9 by esterification using (-)-MPTACl in 70% overall yield.
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    • Other conditions for the asymmetric cyclization, as well as other key precursors, were tried with less success.
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    • (b) For a discussion of the rotameric distributions of several kainoids:
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    • In all known examples, deprotonation of O-allylic carbamates with n-BuLi/sp led to the (S)-configured organolithium compound. For reviews: (a) Hoppe, D. Angw. Chem. 1984, 96, 930; Angw. Chem., Int. Ed. Engl. 1984, 23, 932. (b) Hoppe, D.; Hense, T. Angw. Chem., Int. Ed. Engl. 1997, 36, 2282 and references therein.
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    • In all known examples, deprotonation of O-allylic carbamates with n-BuLi/sp led to the (S)-configured organolithium compound. For reviews: (a) Hoppe, D. Angw. Chem. 1984, 96, 930; Angw. Chem., Int. Ed. Engl. 1984, 23, 932. (b) Hoppe, D.; Hense, T. Angw. Chem., Int. Ed. Engl. 1997, 36, 2282 and references therein.
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  • 40
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    • note
    • 1H NMR exhibits two broad singlets at 4.62 and 4.91 ppm for the alkene protons, indicating the C3-C4 cis relationship (see refences 4i and 12). The NOE studies were carried out at low temperature because of the broad signals.


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