Mild and selective base-free C–H arylation of heteroarenes: experiment and computation†
Hannes P. L. Gemoets,Indrek Kalvet,Nico Erdmann,Volker Hessel,Franziska Schoenebeck,Timothy Noël
Chemical Science Pub Date : 09/05/2016 00:00:00 , DOI:10.1039/C6SC02595A
Abstract

A mild and selective C–H arylation strategy for indoles, benzofurans and benzothiophenes is described. The arylation method engages aryldiazonium salts as arylating reagents in equimolar amounts. The protocol is operationally simple, base free, moisture tolerant and air tolerant. It utilizes low palladium loadings (0.5 to 2.0 mol% Pd), short reaction times, green solvents (EtOAc/2-MeTHF or MeOH) and is carried out at room temperature, providing a broad substrate scope (47 examples) and excellent selectivity (C-2 arylation for indoles and benzofurans, C-3 arylation for benzothiophenes). Mechanistic experiments and DFT calculations support a Heck–Matsuda type coupling mechanism.

Graphical abstract: Mild and selective base-free C–H arylation of heteroarenes: experiment and computation