Synthesis 2014; 46(17): 2272-2282
DOI: 10.1055/s-0034-1378514
feature article
© Georg Thieme Verlag Stuttgart · New York

Preparation of the Zinc Enolate Equivalent of Amides by Zinciomethylation of Isocyanates: Catalytic Asymmetric Reformatsky-Type Reaction

Ryosuke Haraguchi
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyotodaigaku-Katsura, Nishikyo, Kyoto 615-8510, Japan   Fax: +81(75)3832438   eMail: matsubara.seijiro.2e@kyoto-u.ac.jp
,
Seijiro Matsubara*
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyotodaigaku-Katsura, Nishikyo, Kyoto 615-8510, Japan   Fax: +81(75)3832438   eMail: matsubara.seijiro.2e@kyoto-u.ac.jp
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Publikationsverlauf

Received: 02. Juni 2014

Accepted after revision: 25. Juni 2014

Publikationsdatum:
31. Juli 2014 (online)


Abstract

Bis(iodozincio)methane [CH2(ZnI)2] transforms isocyanates (R–N=C=O) into the enolate equivalent of amides via zinciomethylation. The reactivity of the enolate equivalent as a nucleophile toward aldehydes depends on the R group of the isocyanate. For the enolate equivalent formed from phenyl isocyanate, the addition of a catalytic amount of an optically active amino alcohol, which acts as an activator, leads to a catalytic asymmetric Reformatsky-type reaction.

Supporting Information

 
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