Catalytic Synthesis of Bi- and Teraryls in Aqueous Medium with Palladium(II) Complexes of 2-(Pyridine-2-ylmethylsulfanyl)benzoic Acid

摘要: Suzuki–Miyaura coupling reactions of phenylboronic and 1,4-phenylenediboronic acid with ArBr to form bi- teraryls have been efficiently catalyzed by the air- moisture-insensitive complexes [PdCl2L1] [1, L1 = 2-(pyridine-2-ylmethyl)sulfanylbenzoic acid; 0.05–0.5 mol-%] [Pd(L2-H)2] (2, L2-H 2-pyridin-2-yl-benzo[b]thiophen-3-ol; 0.01–0.5 mol-%). The were formed reaction [Pd(CH3CN)2Cl2] L1, catalysis proceeds in water for 1. loading 0.1–0.5 mol-% Pd is very promising teraryls. COOH group imparts solubility 1 water. Ligand L2 unprecedented cyclization course complexation reaction. yield 2 increases time (5 h: 70 %; 24 85 %). two characterized NMR spectroscopy (1H 13C{1H}). single-crystal structures solved, Pd–S, Pd–N, Pd–O bond lengths are 2.269(2), 1.999(6)–2.057(2), 1.9787(17) A, respectively. Nanoparticles (NPs) a narrow size distribution (ca. 3.0–5.5 nm 80–85 % particles) at start these appear be important catalytic coupling. Poisoning experiments two-phase test shown that largely homogeneous involves [Pd0–PdII] processes. angles calculated DFT consistent experimental ones.