Are Organozirconium Reagents Applicable in Current Organic Synthesis?

Ivana Némethová; Radovan Šebesta

doi:10.1055/s-0040-1706055

Synthesis, Table of Contents

Synthesis 2021; 53(03): 447-460
DOI: 10.1055/s-0040-1706055

short review

Are Organozirconium Reagents Applicable in Current Organic Synthesis?

Ivana Némethová ∗

^aUniversity of Basel, Department of Chemistry, St. Johanns-Ring 19, 4056, Basel, Switzerland Email: ivana.nemethova@unibas.ch

,

Radovan Šebesta ∗

^bComenius University in Bratislava, Faculty of Natural Sciences, Department of Organic Chemistry, Mlynská dolina, Ilkovičova 6, 842 15 Bratislava, Slovakia Email: radovan.sebesta@uniba.sk

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Abstract

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Abstract

The search for mild, user-friendly, easily accessible, and robust organometallic reagents is an important feature of organometallic chemistry. Ideally, new methodologies employing organometallics should be developed with respect to practical applications in syntheses of target compounds. In this short review, we investigate if organozirconium reagents can fulfill these criteria. Organozirconium compounds are typically generated via in situ hydrozirconation of alkenes or alkynes with the Schwartz reagent. Alkyl and alkenylzirconium reagents have proven to be convenient in conjugate additions, allylic substitutions, cross-coupling reactions, and additions to carbonyls or imines. Furthermore, the Schwartz reagent itself is a useful reducing agent for polar functional groups.

1 Introduction

2 Synthesis and Generation of the Schwartz Reagent

3 Structure and Properties of Cp₂Zr(H)Cl

4 Reactivity of Organozirconium Reagents

4.1 Asymmetric Conjugate Addition

4.2 Asymmetric Allylic Alkylations

4.3 Desymmetrization Reactions

4.4 Cross-Coupling Reactions

4.5 1,2-Additions

5 Conclusions

Key words

zirconium - Schwartz reagent - hydrometallation - organozirconium reagents

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References

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