Catalyst-Controlled Strategies to Override the Bond Dissociation Energy-Driven Selectivity of Benzylic C(sp³)–H Insertions

Dedicated to John Hartwig on the occasion of his 60^th birthday

Abstract

Catalytic C(sp³)–H insertion reactions of arylalkanes generally proceed at the benzylic position as a consequence of the lower bond dissociation energy (BDE) of the corresponding C–H bond. This account gives a brief overview of recent studies aimed at designing catalyst-controlled amination reactions to go beyond this BDE-driven selectivity. They permit the selective conversion of neutral C–H bonds with a BDE greater than 95 kcal mol^–1 for the formation of alkylamines.

1 Introduction

2 Catalyst-Controlled Site-Selective C–H Insertion Reactions

3 Catalyst-Controlled Intermolecular Amination of Nonactivated C–H Bonds of Arylalkanes

4 Conclusion

Key words

rhodium catalysis - nitrene - amination - C–H functionalization - regioselectivity - C–N bond formation

Publication History

Received: 31 July 2024

Accepted after revision: 10 September 2024

Article published online:
27 September 2024

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