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Relevant academic research and scientific papers

Ligand-free Pd/C-catalyzed Suzuki-Miyaura coupling reaction for the synthesis of heterobiaryl derivatives

We have developed a mild and efficient protocol for the ligand-free and heterogeneous Pd/C-catalyzed hetero Suzuki-Miyaura coupling reaction that allows for the synthesis of both heteroaryl-aryl and heteroaryl-heteroaryl derivatives in good to excellent yields. The Royal Society of Chemistry.

MATERIALS FOR ELECTRONIC DEVICES

The present application concerns compounds for use in electronic devices, processes for preparing the compounds, and electronic devices comprising the compounds.

Palladium (II)–Salan Complexes as Catalysts for Suzuki–Miyaura C–C Cross-Coupling in Water and Air. Effect of the Various Bridging Units within the Diamine Moieties on the Catalytic Performance

Water-soluble salan ligands were synthesized by hydrogenation and subsequent sulfonation of salens (N,N’-bis(slicylidene)ethylenediamine and analogues) with various bridging units (linkers) connecting the nitrogen atoms. Pd (II) complexes were obtained in reactions of sulfosalans and [PdCl4]2?. Characterization of the ligands and complexes included extensive X-ray diffraction studies, too. The Pd (II) complexes proved highly active catalysts of the Suzuki–Miyaura reaction of aryl halides and arylboronic acid derivatives at 80 ?C in water and air. A comparative study of the Pd (II)–sulfosalan catalysts showed that the catalytic activity largely increased with increasing linker length and with increasing steric congestion around the N donor atoms of the ligands; the highest specific activity was 40,000 (mol substrate) (mol catalyst × h)?1. The substrate scope was explored with the use of the two most active catalysts, containing 1,4-butylene and 1,2-diphenylethylene linkers, respectively.

Synthesis of zwitterionic palladium complexes and their application as catalysts in cross-coupling reactions of aryl, heteroaryl and benzyl bromides with organoboron reagents in neat water

N-(3-Chloro-2-quinoxalinyl)-N′-arylimidazolium salts (aryl = 2,6-diisopropylphenyl [HL1Cl]Cl, aryl = mesityl [HL2Cl]Cl) have been synthesized by treating 2,3-dichloroquinoxaline with the corresponding N′-arylimidazole in neat water. Facile reactions of these imidazolium salts with Pd(PPh3)4 and Pd2(dba)3/PPh3 (dba = dibenzyledene acetone) at 50 °C have afforded zwitterionic palladium(ii) complexes [Pd(HL1)(PPh3)Cl2] (I) and [Pd(HL2)(PPh3)Cl2] (II) in excellent yields. I and II have been tested for their ability to catalyze Suzuki-Miyaura cross coupling (SMC) reactions in neat water/K2CO3 and are found to be highly active for carrying out these reactions between aryl bromides and organoboron reagents. Furthermore, the scope of the catalyst I was also examined by employing (hetero)aryl bromides, hydrophilic aryl bromides, benzyl bromides and various organoboron reagents. More than 80 aryl/benzyl bromide-arylboronic acid combinations were screened in neat water/K2CO3 and it was found that I was a versatile catalyst, which produced biaryls/diarylmethanes in excellent yields. A TON of 82 000 was achieved by using I. Studies on the mechanism have also been carried out to investigate the involvement of carbene complexes in the catalytic path. Poison tests and a two-phase test were also conducted and the results are reported.

A Zwitterionic Palladium(II) Complex as a Precatalyst for Neat-Water-Mediated Cross-Coupling Reactions of Heteroaryl, Benzyl, and Aryl Acid Chlorides with Organoboron Reagents

The Suzuki–Miyaura cross-coupling (SMC) reactions of several heteroaryl chlorides, benzyl chlorides, and aryl acid chlorides with (hetero)arylboron reagents have been investigated in the presence of [Pd(HL1)(PPh3)Cl2] (I) [HL1 = 3-[(2,6-diisopropylphenyl)-1-imidazolio]-2-quinoxalinide] as catalyst and K2CO3 as base in neat water. The synthesis of the heterocycle-containing biaryls required the addition of 2 mol-% of a phosphine ligand (PPh3 or X-Phos). A combination of more than 115 substrates were screened and it was found that I is a versatile catalyst that can produce heterocycle-containing biaryls, diarylmethanes, and benzophenones in moderate-to-excellent yields.

Photoluminescence color tuning of phosphorescent bis-cyclometalated iridium(III) complexes by ancillary ligand replacement

A series of bis-cyclometalated iridium(III) complexes bearing various types of 1,3-diketonate ancillary ligands were prepared, and their photoluminescent (PL) properties were investigated, especially focusing on the emission color tuning. When the dipivaloylmethanate ancillary ligand (O^O-1a) was replaced by conjugated 1,3-diketonates such as 1,3-bis(3,4-dibutoxyphenyl)propane-1,3- dionate (O^O-1b) and 1,3-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)propane-1,3- dionate (O^O-1c), the blue-emitting bis[2-(3,5-bis(trifluoromethyl)phenyl) pyridinato-N,C2′]iridium(III) (Ir-1) and bluish green-emitting bis[2-phenylpyridinato-N,C2′]iridium(III) (Ir-2) complexes exhibited significantly red-shifted phosphorescence in solution (λPL; 474-604 nm and 521-661 nm for Ir-1a-c and Ir-2a-c, respectively: the subscripts a, b, and c corresponding to O^O-1a-c). On the other hand, the ancillary ligand replacement was less effective on tuning the emission color of the green-emitting bis[2-(2,4-bis(trifluoromethyl)phenyl) pyridinato-N,C2′]iridium(III) complex (λPL; 541-566 nm for Ir-3a-c), and no PL color change was observed for the red-emitting bis[1-(dibenzo[b,d]furan-4-yl)isoquinolinato-N, C3′]iridium(III) complex (Ir-4). The X-ray crystallographic analysis for Ir-1a-c revealed that these complexes adopt cis-C,C and trans-N,N configuration, indicating that the coordination geometry around the iridium center is not a main factor for the emission spectral differences caused by the O^O ancillary ligands. Furthermore, the ancillary ligand effect on the PL properties of the present iridium(III) complexes is independent on solvent polarity and concentrations. Taking these results into consideration, the ancillary ligand effect should be attributed to the electronic structures of the complexes, and the inter-ligand energy transfer from the triplet metal-to-ligand charge transfer level at the cyclometalated ligand (3MLCTC^N) to the ancillary ligand-related triplet level (3LCO^O or 3MLCTO^O) should play a significant role in the triplet exciton formation. The PL properties of Ir-1-Ir-4 in PMMA films were also investigated, and the remarkable blue shifts of λPLs due to rigidochromism were observed for Ir-1b,c and Ir-2b,c that have the aromatic O^O ancillary ligands. It was found that some of the complexes developed here exhibited larger ΦPLs in PMMA films than in toluene solutions.

Ligand-free and heterogeneous palladium on carbon-catalyzed hetero-suzuki-miyaura cross-coupling

A ligand-free and heterogeneous palladium on carbon (Pd/C)-catalyzed hetero-SuzukiMiyaura coupling reaction has been developed. The protocol enables the construction of both heterocyclic-alicyclic and heterocyclic-heterocyclic biaryl derivatives in good to excellent yields. Furthermore, Pd/C could be reused. The time-course study clarified that palladium was leached into the reaction media as the reaction proceeded and then completely deposited on the carbon support.