Unprecedented Access to β‐Arylated Selenophenes through Palladium‐Catalysed Direct Arylation

Several reported methods allow access to α‐arylated selenophenes, whereas the synthesis of β‐arylated selenophenes remains very challenging. Here, the Pd‐catalysed coupling of benzenesulfonyl chlorides with selenophenes affording regiospecific β‐arylated selenophenes is reported. The reaction proceeds with easily accessible catalyst, base and substrates, and tolerates a variety of substituents both on the benzene and selenophene moieties. This transformation allows the programmed synthesis of polyarylated selenophenes with potential applications in pharmaceutical and materials chemistry, as the installation of aryl groups at the desired positions can be achieved. β‐Regioselectivity: The palladium‐catalysed coupling of benzenesulfonyl chlorides with selenophene derivatives allows the access to β‐arylated selenophenes with complete regioselectivity. The reaction proceeds with easily accessible catalyst, base and substrates, without oxidant and tolerates a variety of substituents both on the benzene and selenophene moieties.