A highly active catalytic system for Suzuki–Miyaura cross-coupling reactions of aryl and heteroaryl chlorides in water

Abstract

An easily available Pd(OAc)(2)/(2-mesitylindenyl)dicyclohexylphosphine/Me(octyl)(3)N(+)Cl(-)/K(3)PO(4)·3H(2)O catalytic system was developed and it shows high catalytic activity in the Suzuki-Miyaura cross-coupling reaction of a diverse array of aryl and heteroaryl chlorides in water. Notably, this catalytic system also works with ultra-low loading of the catalyst with high turnover numbers.

Palladium-Catalyzed Suzuki Reactions in Water with No Added Ligand: Effects of Reaction Scale, Temperature, pH of Aqueous Phase, and Substrate Structure

“…However, the limited solubility of the halogenated substrates and ligands in water often leads to slow rate and low yields. To overcome this limitation, alternative methodologies using water-soluble ligands, [52][53][54][55][56] organic co-solvents, [25][26][27][28][29][30][31][32] phase-transfer catalysts 33,[48][49][50][51] and inorganic salt promoters, 34,35 and heating with microwave or ultrasound were reported. [36][37][38][39][40] In 1989, Bumagin et al 57 were the first to report a Pd(OAc) 2 catalyzed Suzuki reaction of phenylboronic acid with aryl iodides containing a -OH or -COOH substituents; Na 2 CO 3 was employed as the base in neat water under an argon atmosphere.…”

Synthesis and Reactions of Halo-substituted Alkylthiophenes. A Review

“…47 In their study, Pd(PPh 3 ) 4 was compared with an electron-rich version tris[tri(2-thienyl)phosphine)palladium) or (Pd(PTh 3 ) 4 ), and it was found that the latter catalytic system resulted . 48 The authors reported yields over 80% when using the commercially available ligand L1. After optimizing the phase transfer agent (tetra-nbutylammonium bromide or Me(octyl) 3 N C Cl ¡ ), the base (K 3 PO 4 H 2 O, KOAc, KOH, K 2 CO 3 , Na 2 CO 3 , NaOH, Cs 2 CO 3 ) and time (1 or 8 h), a 98% yield was achieved on a model system.…”

Efficient Suzuki–Miyaura C-C Cross-Couplings Induced by Novel Heterodinuclear Pd-bpydc-Ln Scaffolds

“…This synthesis approach has revolutionized the production of advanced materials [15,16,17,18], pharmaceuticals [19,20,21], agrochemicals [21,22], liquid crystals [23], and natural or biologically active compounds [24,25,26,27,28], etc. Numerous attractive strategies have been developed to address the ample scope of this catalytic process including the utilization of palladium nanoparticles [29,30,31,32,33,34,35], or palladium immobilized on magnetic nanoparticles [36] and natural supports [37], use of nucleophilic carbene ligands (mostly NHCs) [38,39,40,41,42,43,44,45,46], Schiff bases [47,48], water-soluble ligands like poly(ethylene glycol)-functionalized N-heterocyclic carbenes [49], thiourea [50] or phosphines [51,52], induction by microwave (MW) acceleration [53,54], use of “greener” solvents, such as water [55,56,57,58,59,60,61,62,63,64,65] (activated by MW [66,67] or in catalysis under micellar conditions [68] for enhancing the solubility of the aromatic halide), water–DMF […”