Transition-Metal-Catalyzed C(sp³)–C(sp³) Cross-Coupling to Construct All-Carbon Quaternary Carbon Centers

Abstract

Transition-metal-catalyzed C(sp³)–C(sp³) cross-coupling reactions represent a powerful strategy for constructing all-carbon quaternary centers. However, these reactions remain challenging due to significant steric hindrance effects and the propensity for side reactions such as elimination and isomerization. This review provides a comprehensive summary of the progress made over the past few decades in the construction of all-carbon quaternary centers, with a focus on coupling reactions involving tertiary C(sp³) and primary/secondary C(sp³) centers [as the cross-coupling of two tertiary C(sp³) centers remains unsuccessful]. The discussion is organized around reaction conditions, substrate scope, and reaction mechanisms, and a brief overview of transformations based on these coupling reactions is also presented.

1 Introduction

2 3° C(sp³)–1° C(sp³) Cross-Coupling

2.1 Cobalt Catalysis

2.2 Copper Catalysis

2.3 Nickel Catalysis

2.4 Iron Catalysis

2.5 Other Catalysis

3 3° C(sp³)–2° C(sp³) Cross-Coupling

3.1 Copper Catalysis

3.2 Iron Catalysis

4 Conclusion

Key words

transition metal catalysis - coupling reactions - C(sp³)–C(sp³) coupling - all-carbon quaternary carbon centers - nucleophiles - electrophiles

Publication History

Received: 24 August 2024

Accepted after revision: 14 October 2024

Accepted Manuscript online:
14 October 2024

Article published online:
18 November 2024

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