Direct catalytic arylation of heteroarenes with meso-bromophenyl-substituted porphyrins

Alexei Nikolaevich Kiselev; Olga Konstantinovna Grigorova; Alexei Dmitrievich Averin; Sergei Aleksandrovich Syrbu; Oskar Iosifovich Koifman; Irina Petrovna Beletskaya

doi:10.3762/bjoc.13.152

Direct catalytic arylation of heteroarenes with meso-bromophenyl-substituted porphyrins

Beilstein J Org Chem. 2017 Aug 3:13:1524-1532. doi: 10.3762/bjoc.13.152. eCollection 2017.

Authors

Alexei Nikolaevich Kiselev¹, Olga Konstantinovna Grigorova², Alexei Dmitrievich Averin², Sergei Aleksandrovich Syrbu¹, Oskar Iosifovich Koifman³, Irina Petrovna Beletskaya²

Affiliations

¹ G. A. Krestov Institute of Solution Chemistry RAS, Akademicheskaya ul., Ivanovo, 153045, Russia.
² Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1-3, Moscow, 119991, Russia.
³ Ivanovo State University of Chemistry and Technology, 7 Sheremetyevskii prosp., Ivanovo, 153000, Russia.

Abstract

The arylation of mono-, di- and tetra-meso-bromophenyl-substituted porphyrins with the heteroarenes containing "acidic" C-H bonds, such as benzoxazole, benzothiazole and N-methylimidazole was studied in the presence of three alternative catalytic systems: Pd(dba)₂/DavePhos/Cs₂CO₃, Pd(PPh₃)₄/PivOH/K₂CO₃ and Pd(OAc)₂/Cu(OAc)₂/PPh₃/K₂CO₃. The first catalytic system was found to be successful in the reaction with benzoxazole, the second one was less efficient for our purpose, while the third system proved to be most versatile and afforded corresponding mono-, di-, tri- and even tetraarylated derivatives of porphyrins.

Keywords: arylation; copper catalysis; heteroarenes; palladium catalysis; porphyrins.