Divergent Carbocyanation and Hydrocyanation of Alkynes Enabled by Photoinduced Nickel-Catalyzed Homolytic Bond Cleavage of C(sp³)–N Bond in Isonitriles

Abstract

Catalytic strategies for breaking and forming chemical bonds are longstanding goals in chemical synthesis. However, the activation of inert chemical bonds remains a significant challenge. Recently, our group successfully developed a C(sp³)–N bond homolytic activation strategy for isonitriles by using an in situ-generated electronically active nickel complex. This strategy bypasses the thermodynamically unfavorable two-electron or one-electron oxidative addition process, allowing us to invent an unprecedented ‘cut-and-sew’ reaction using isonitriles and alkynes. This transformation proceeds under simple and mild conditions, demonstrating a broad substrate scope with excellent functional-group compatibility and atom economy. Moreover, we applied this activation mode to develop a selective hydrocyanation of alkynes with isonitriles as cyanating agents in the presence of an exogenous photocatalyst.

1 Introduction

2 Discovery of the Photoactivation Process of Nickel–Isonitrile Complexes

3 Photoinduced Nickel-Catalyzed Cut-and-Sew Reaction of Isonitriles and Arylalkynes

4 Dual Nickel/Photoredox-Catalyzed Hydrocyanation of Alkynes with Isonitriles

5 Proposed Reaction Pathways

6 Conclusion and Perspectives

Key words

C(sp³)–N bond activation - nickel catalysis - hydrocyanation - alkynes - isonitriles - photocatalysis

Publikationsverlauf

Eingereicht: 25. Februar 2025

Angenommen nach Revision: 01. April 2025

Accepted Manuscript online:
01. April 2025

Artikel online veröffentlicht:
14. Mai 2025

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