Nickel-Catalyzed Enantioconvergent C(sp³)–C(sp³) Cross-Coupling between α-Iodogermanes and Alkylzinc Reagents

Dedication

Dedicated to Professor Paul Knochel on the occasion of his 70th birthday.

Abstract

We report a nickel-catalyzed enantioconvergent C(sp³)–C(sp³) cross-coupling between α-iodogermanes and alkylzinc reagents to access α-chiral alkylgermanes. This transformation, a strategy previously established for silicon-based electrophiles, extends to germanium, enabling the enantioselective formation of α-chiral germanes from simple, unactivated alkyl chains. While yields and enantioselectivities remain moderate, the reaction outcome was finely tuned through the design and evaluation of a library of over 30 ligands, including more than a dozen novel scaffolds. Notably, two distinct NiBr₂∙PyBox complexes allowed for access to products of opposite absolute configuration, and preformed nickel complexes were required to reach synthetically useful conversions. These findings highlight the challenges of asymmetric catalysis with heavier main-group elements and provide a platform for the future design of ligands tailored to organogermanium chemistry.

Keywords

Asymmetric catalysis - C(sp³)–C(sp³) cross-coupling - Enantioconvergence - Germanium - Nickel

Publication History

Received: 15 June 2025

Accepted after revision: 25 June 2025

Accepted Manuscript online:
25 June 2025

Article published online:
18 August 2025

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