Recent Advances in Cross-Couplings of Functionalized Organozinc Reagents

Dedicated to the memory of Victor Snieckus, a pioneer of organometallic chemistry and missing friend

Abstract

Cross-couplings involving organozinc reagents usually require a Pd-catalyst (Negishi cross-coupling), however, uncatalyzed cross-couplings of zinc organometallics proceed well in the absence of transition-metal catalysts with reactive electrophiles such as benzal 1,1-diacetates, benzhydryl acetates, and iminium trifluoroacetates. Organozinc compounds also undergo C–N bond formation with O-benzoylhydroxylamines or organic azides in the presence of cobalt- or iron-catalysts. Highly diastereoselective and enantioselective cross-couplings can be readily performed with room-temperature configurationally stable alkylzinc species, producing diastereoselectively and enantiomerically enriched products. Finally, highly regioselective magnesiations of functionalized arenes and heteroarenes undergo Negishi (after transmetalation with ZnCl₂) or Cu-catalyzed cross-couplings.

1 Introduction

2 Uncatalyzed Cross-Couplings of Organozinc Reagents with Highly Electrophilic Partners

3 Iron- and Cobalt-Catalyzed Aminations using Organozinc Reagents

4 Stereo- and Regioselective Cross-Couplings of Organozinc Reagents

5 Conclusion

Key words

cross-coupling - organozinc reagents - carbon–carbon bond formation - carbon–nitrogen bond formation - amination - diastereoselective reaction - enantioselective reaction

Publication History

Received: 29 July 2021

Accepted after revision: 16 August 2021

Accepted Manuscript online:
16 August 2021

Article published online:
12 October 2021

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