Design of Molecular Transformations Based on the Concerted Function of Two Zinc Atoms in Bis(iodozincio)methane

Mutsumi Sada; Masanobu Uchiyama; Seijiro Matsubara

doi:10.1055/s-0034-1379250

Synlett, Table of Contents

Synlett 2014; 25(20): 2831-2841
DOI: 10.1055/s-0034-1379250

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Design of Molecular Transformations Based on the Concerted Function of Two Zinc Atoms in Bis(iodozincio)methane

Mutsumi Sada

^aDepartment of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyotodaigaku-katsura, Nishikyo, 615-8510 Kyoto, Japan Fax: +81(075)3832438 Email: matsubara.seijiro.2e@kyoto-u.ac.jp

,

Masanobu Uchiyama

^bGraduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, 113-0033 Tokyo, Japan

,

Seijiro Matsubara*

^aDepartment of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyotodaigaku-katsura, Nishikyo, 615-8510 Kyoto, Japan Fax: +81(075)3832438 Email: matsubara.seijiro.2e@kyoto-u.ac.jp

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Abstract

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Abstract

Bis(iodozincio)methane, prepared from diiodomethane and zinc metal in the presence of a lead catalyst, is capable of performing several unique molecular transformations. It can operate not only as a dianion, but also as a bidentate Lewis acid. In this account, the methylenation of carbonyl compounds, nucleophilic cyclopropanation reactions, 1,4-addition reactions of bis(iodozincio)methane, and reduction reactions of π-allylpalladium are discussed, along with the associated density functional theory calculations.

1 Introduction

2 Methylenation of Carbonyl Compounds

3 Nucleophilic Cyclopropanation

3.1 Cyclopropanation of 1,2-Diketones

3.2 Asymmetric Construction of Quaternary Carbon Atoms by Stereospecific Cyclopropanation

4 1,4-Addition Reactions of Bis(iodozincio)methane

4.1 Three-Atom Ring-Contraction Reaction

4.2 Enolate–Homoenolate Intermediates and Their Reactions

5 Reduction of π-Allylpalladium Derivatives

6 Conclusions and Outlook

Key words

zinc - dizinc - cyclopropanation - oxy-Cope rearrangement - 1,4-addition - organometallic reagents - ring contractions - π-allylpalladium

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References

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