Unraveling the C−H Arylation of Benzo‐Fused Cycloalkanones: Combined Experimental and Computational Evidence - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Advanced Synthesis and Catalysis Année : 2021

Unraveling the C−H Arylation of Benzo‐Fused Cycloalkanones: Combined Experimental and Computational Evidence

Benjamin Large
Damien Prim

Résumé

The C-H functionalization of benzo-fused cycloalkanones represents a synthetic challenge since such scaffolds display different activation sites, at sp 2 and sp 3 carbons, a bicyclic structure and various sizes of the cycloalkanone ring. Anticipating the outcome of C-H functionalization and the impact of the presence and size of the cycloalkanone ring would help to foresee synthetic routes to more complex molecular architectures. The mechanism of C-H arylation was studied using DFT calculations for tetralone, benzosuberone and indanone and compared to acetophenone. Comparison of energetic profiles allowed identifying key steps of the process. Analysis of the topology of key intermediates allowed correlating the deformation of palladacycles to the potential reactivity of the benzo-fused cycloalkanone family members. The experimental results were in full agreement with the trend provided by the theoretical study. A wide panel of diversely substituted benzo-fused cycloalkanones has been successfully obtained using optimized conditions. Moreover, an approach towards polycyclic molecules has been illustrated featuring a C-H arylation and a second step taking advantage of the remaining ketone fragment and its ability to undergo diverse transformations leading to alternative pathways to more complex molecular architectures

Domaines

Chimie
Fichier principal
Vignette du fichier
HAL-benjaminLarge-ILV.pdf (1.03 Mo) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)

Dates et versions

hal-03161541 , version 1 (07-03-2021)

Identifiants

Citer

Benjamin Large, Damien Prim. Unraveling the C−H Arylation of Benzo‐Fused Cycloalkanones: Combined Experimental and Computational Evidence. Advanced Synthesis and Catalysis, inPress, ⟨10.1002/adsc.202001349⟩. ⟨hal-03161541⟩
30 Consultations
59 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More