Imidazole, pyrimidine and diazepine containing heteroaryl-substituted heterocyclic salts as efficient ligand precursors for Mizoroki–Heck coupling reaction: synthesis, structural characterization and catalytic activities

Abstract

The nine new heteroaryl-substituted imidazolidinium (1a–c), pyrimidinium (2a–c) and diazepinium (3a–c) salts as N-heterocyclic carbene (NHC) precursors were synthesized in good yields and entirely characterized using elemental analyses and conventional spectroscopic methods. In situ formed complexes from heterocyclic salts (1–3), Pd(OAc)2 and in the presence of KOBut as a base were tested as catalysts for the Mizoroki–Heck coupling reaction in an aqueous media and very high yields were achieved. 1,3-Di(5-methylthiophen-2-ylmethyl)pyrimidinium hexafluorophosphate salt (2b) was structurally characterized by single-crystal X-ray diffraction. In the 2b compound (C16H21N2S2)+[PF6]−, the terminal thiophene rings are twisted with a dihedral angle of 72.8(3)°. In the pyrimidine ring, the three successive C atoms between the N atoms are disordered over two positions [occupancy ratio 0.753(12):0.247(12)]. In the crystal, neighboring molecules are linked by C–H…F hydrogen bonds, running along the b axis.