Article Dans Une Revue Organic Chemistry Frontiers Année : 2023

Double C-H bond functionalization for C-C coupling at the beta-position of thiophenes using palladium-catalyzed 1,4-migration associated with direct arylation

Résumé

The functionalization of C-H bonds at beta-positions of 5-membered ring heteroarenes such as thiophene is generally more challenging than at alpha-positions. By using Pd-catalyzed 1,4-migration associated with direct arylation, under appropriate conditions, the functionalization of such thienyl beta-positions of 2-arylthiophenes is possible. The oxidative addition of 2-(2-bromoaryl)thiophenes to palladium followed by Pd 1,4-migration activates these beta-positions. Then, Pd-catalyzed direct coupling with heteroarenes provides beta-heteroarylated 2-arylthiophene derivatives. In the course of this coupling reaction, a new C-C bond arises from the functionalization of two C-H bonds. Conversely, the Suzuki reaction using such 2-(2-bromoaryl)thiophenes provides 1,2-diheteroaryl-substituted benzene derivatives. These regiodivergent heteroarylations tolerate a range of substituents on the benzene ring and also several heteroarenes and provide a new route to pi-extended polycyclic heteroaromatics. Moreover, these procedures employ easily available air-stable catalysts and inexpensive bases.

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hal-04019591 , version 1 (30-05-2023)

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Linhao Liu, Marie Cordier, Thierry Roisnel, Henri Doucet. Double C-H bond functionalization for C-C coupling at the beta-position of thiophenes using palladium-catalyzed 1,4-migration associated with direct arylation. Organic Chemistry Frontiers, 2023, ⟨10.1039/d3qo00018d⟩. ⟨hal-04019591⟩
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