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Three-Carbon Homologation of Diorganozincs with Lithiated Acetylenic Epoxides

  作者 DENICHOUX AURELIEN; DEBIEN LAURENT; CYLDINSKY MATHIEU; KACI MALIKA; CHEMLA FABRICE; FERREIRA FRANCK; PEREZLUNA ALEJANDRO  
  选自 期刊  Journal of Organic Chemistry;  卷期  2013年78-1;  页码  134-145  
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[摘要]Reaction of dialkylzincs with lithiated acetylenic epoxides is described to give zincates that undergo a 1,2-metallate rearrangement by an anti-S(N)2' pathway. This rearrangement occurs with the transfer of an alkyl or a silyl group affording allenylzinc intermediates. Allenic and/or homopropargylic alcohols are obtained upon hydrolysis. Quenching the reaction mixture with aldehydes or ketones is shown to give access to 2-alkynyl-1,3-diols in a stereoselective manner.

 
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