Solid Organozinc Pivalates: A New Class of Zinc Organometallics with Greatly Enhanced Air- and Moisture-Stability

Dedicated to Prof. Herbert Mayr on the occasion of his 70^th birthday

Abstract

Organozinc species are powerful reagents for performing carbon–carbon and carbon–heteroatom bond-forming reactions in the presence of a transition-metal catalyst. However, extended applications of zinc reagents have been hampered by their moderate air- and moisture­-stability. This short review presents our recent developments on the preparation of solid aryl, benzyl, heteroaryl, allyl zinc pivalates and zinc amide enolate reagents with greatly enhanced stability toward to air and moisture.

1 Introduction

2 Preparation of Organozinc Pivalates

2.1 Using Organic Halides as Substrates

2.2 Using a Directed Metalation on Functionalized Arenes and Heteroarenes

2.3 Preparation of Solid Allylic Zinc Pivalates

3 General Reactivity Patterns of Organozinc Pivalates

3.1 General Aspects

3.2 Transition-Metal-Catalyzed Cross-Couplings

3.3 Other Carbon–Carbon Bond-Forming Reactions Using Organozinc Pivalates

3.4 Preparation and Reactions of Solid, Salt-Stabilized Zinc Amide Enolates as New, Convenient Reformatsky Reagents

4 Conclusion

Key words

zinc - magnesium - cross-coupling - transition metal - metalation

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