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

Ryosuke Haraguchi; Seijiro Matsubara

doi:10.1055/s-0034-1378514

Synthesis, Table of Contents

Synthesis 2014; 46(17): 2272-2282
DOI: 10.1055/s-0034-1378514

feature article

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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Abstract

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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.

Key words

organozinc reagents - dizinc compounds - Reformatsky reaction - asymmetric synthesis - catalysis

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References

References

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