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

Erwan Brunard; Vincent Boquet; Théo Bissonnier; Tanguy Saget; E. Daiann Sosa Carrizo; Marie Sircoglou; Philippe Dauban

doi:10.1055/s-0043-1775407

Synlett, Table of Contents

Synlett 2025; 36(06): 630-636
DOI: 10.1055/s-0043-1775407

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

Erwan Brunard

^aUniversité Paris-Saclay, CNRS, Institut de Chimie des Substances Naturelles, UPR 2301, 91198 Gif-sur-Yvette, France

,

Vincent Boquet

^aUniversité Paris-Saclay, CNRS, Institut de Chimie des Substances Naturelles, UPR 2301, 91198 Gif-sur-Yvette, France

,

Théo Bissonnier

^aUniversité Paris-Saclay, CNRS, Institut de Chimie des Substances Naturelles, UPR 2301, 91198 Gif-sur-Yvette, France

,

Tanguy Saget

^aUniversité Paris-Saclay, CNRS, Institut de Chimie des Substances Naturelles, UPR 2301, 91198 Gif-sur-Yvette, France

,

E. Daiann Sosa Carrizo

^bUniversité Paris-Saclay, CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay, 91400 Orsay, France

,

Marie Sircoglou∗

^bUniversité Paris-Saclay, CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay, 91400 Orsay, France

,

Philippe Dauban∗

^aUniversité Paris-Saclay, CNRS, Institut de Chimie des Substances Naturelles, UPR 2301, 91198 Gif-sur-Yvette, France

› Author Affiliations

Abstract

All articles of this category

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

Full Text

References

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