87573-07-7

Upstream product

• 1008-89-5 2-phenylpyridine 
• 3240-34-4 [bis(acetoxy)iodo]benzene 
• 108-24-7 acetic anhydride 
• 598-55-0 methyl carbamate 
• 110-86-1 pyridine 
• 5957-89-1 2-(2-methoxy-phenyl)-pyridine 
• 90-04-0 2-methoxy-phenylamine 
• 109-04-6 2-bromo-pyridine 
• 98-80-6 phenylboronic acid 
• 10581-12-1 tetramethyl ammonium acetate 
• 6597-18-8 (dibenzoyloxyiodo)benzene 
• 64-19-7 acetic acid 
• 33421-36-2 2-(pyridine-2-yl)phenol 

Downstream Products

• 33421-36-2 2-(pyridine-2-yl)phenol 
• 1571060-33-7 2-(2-acetoxy-5-tosylphenyl)pyridine 

Relevant academic research and scientific papers

Benzoato and thiobenzoato ligands in the synthesis of dinuclear palladium(III) and -(II) compounds: Stability and catalytic applications

New palladium(III) compounds of formula Pd2[(C6H4)PPh2]2[OXC(C6H5)]2Cl2 [3a (X = O); 3b (X = S)] were obtained by the oxidation of the analogous palladium(II) ones with PhICl2 and were characterized by 31P, 1H, and 13C NMR spectroscopy at 223 K. Compound 3a was also structurally characterized by single-crystal X-ray diffraction methods, which revealed a Pd-Pd distance of 2.5212(10) ?. DFT calculations were conducted to study the stability of all of these new palladium(III) and -(II) compounds with focus on the influence of the O虠S substitution of the donor atom in the ligand. The palladium(II) compounds Pd2[(C6H4)PPh2]2[OXC(C6H5)]2 [2a (X = O), 2b (X = S)] were also tested as precatalyst in two reactions: (1) the acetoxylation of 2-phenylpyridine and (2) the room-temperature 2-phenylation of indoles. Compound 2b is a better precatalyst than 2a in the first reaction (4 h; isolated yield, 67.5 vs. 50.4 %). In the second catalytic reaction, isolated yields of 97 (10 h, substrate: 1-methylindole) and 99 % (24 h, substrate: indole) were obtained with 2a as the precatalyst, whereas 2b gave low or no conversion. Dinuclear palladium(III) and -(II) compounds with benzoato and thiobenzoato ligands are synthesized. DFT calculations are performed to study the stability of these compounds and the influence of the O虠S substitution of the donor atom. The catalytic activity of the palladium(II) complexes is also tested in the acetoxylation of 2-phenylpyridine and the room-temperature 2-phenylation of indoles.

Palladium-Catalyzed C-H Bond Acetoxylation via Electrochemical Oxidation

Here we describe the development of a method for the Pd-catalyzed electrochemical acetoxylation of C-H bonds. The oxidation step of the catalytic cycle is probed through cyclic voltammetry and bulk electrolysis studies of a preformed palladacycle of 8-methylquinoline. A catalytic system for C-H acetoxylation is then developed and optimized with respect to the cell configuration, rate of oxidation, and chemistry at the counter electrode. This transformation is then applied to substrates containing various directing groups and to the acetoxylation of both C(sp2)-H and C(sp3)-H bonds.

Hypercrosslinked Polymer Platform-Anchored Single-Site Heterogeneous Pd-NHC Catalysts for Diverse C-H Functionalization

We demonstrate a new class of hypercrosslinked polymer (HCP) platform-Anchored single-site heterogenized Pd-NHC catalysts for multipurpose C-H functionalization reactions. This new class is represented by a set of three catalysts, viz., HCP-B-MeNHC-Pd, HCP-B-BnNHC-Pd, and HCP-TPM-MeNHC-Pd, having a variation on the structural feature of the anchoring polymeric platform. All three catalysts were fully characterized via diverse solid-state characterization and analytical techniques such as X-ray photoelectron spectroscopy, 13C cross-polarization magic-Angle-spinning nuclear magnetic resonance, field-emission scanning electron microscopy, energy-dispersive X-ray analysis, thermogravimetric analysis, and inductively coupled plasma-optical emission spectrometry. Three types of regularly practiced and very useful C-H functionalization reactions, viz., C-H halogenation, acetoxylation, and arylation, are tested with the new catalysts and found to be highly compatible and successful. With the HCP-TPM-MeNHC-Pd catalyst, up to 85, 75, and 70% yields of the functionalized products were achieved for the halogenation, acetoxylation, and arylation reactions, respectively. Demanding attributes such as enhanced activity, heterogeneity, and recyclability are offered by this new system, making it a promising candidate in the field of heterogeneous C-H functionalization, where only a few efficient catalysts are available.

Rhodium(III)-Catalyzed Selective C-H Acetoxylation and Hydroxylation Reactions

An efficient Cp?Rh(III)-catalyzed, chelation-assisted C(sp2)-H acetoxylation and hydroxylation reaction has been developed for the first time. The reaction proceeds under mild conditions and allows for selective preparation of C-H acetoxylation

Directed Aromatic C-H Activation/Acetoxylation Catalyzed by Pd Nanoparticles Supported on Graphene Oxide

The first solid-supported directed aromatic C-H activation/acetoxylation has been successfully developed by using palladium nanoparticles supported on graphene oxide (PdNPs/GO) as a catalyst. The practicability of this method is demonstrated by simple preparation of catalyst, high catalytic efficiency, wide functional group tolerance, and easy scale up of the reaction. A hot filtration test and Hg(0) poisoning test indicate the heterogeneous nature of the catalytic active species.

Ligand Control in Selective C–H Oxidative Functionalization Using Pd-PEPPSI-Type Complexes

To achieve high selectivity in directed C–H activation, an NHC ligand was introduced to a palladium catalyst. A range of Pd-PEPPSI complexes were applied in the direct acetoxylation of 2-phenylpyridine. The best catalyst was found to be the one based on a

COMPLEXES AND CATALYTIC PROCESSES

The present application is directed towards complexes of formula (I), to methods for preparing such complexes, and to use of such complexes in catalysis. The complexes show utility in a range of catalytic cycles, including Pd(ll)/Pd(IV) cycles. (Formula (I))

Chelating Bis-N-heterocyclic Carbene-Palladium(II) Complexes for Oxidative Arene C-H Functionalization

Bis-N-heterocyclic carbene (NHC)-chelated palladium(II) complexes have been synthesized, characterized fully including single-crystal X-ray structural analyses, and utilized for the first time toward catalytic oxidative C-H functionalization of arenes with PhI(OAc)2 and N-bromosuccinimide. (Figure Presented).

Palladium catalyzed ortho-C-H-benzoxylation of 2-arylpyridines using iodobenzene dibenzoates

A palladium-catalyzed ortho-C-H-benzoxylation of 2-arylpyridines using iodobenzene dibenzoates has been developed. The reaction employed the stable and easily accessible hypervalent iodine reagents as both benzoxylate source and oxidant which made the protocol simple and facile. It showed high regioselectivity and good functional group tolerance, and gave the mono-benzoxylation products in moderate to excellent yields.

Selective N -Chelation-directed C-H activation reactions catalyzed by pd(II) nanoparticles supported on multiwalled carbon nanotubes

N-Chelation-directed C-H activation reactions that utilize the Pd(II)/Pd(IV) catalytic cycle have been previously reported. To date, these reactions employ only homogeneous palladium catalysts. The first use of a solid-supported Pd(II) catalyst [Pd(II) nanoparticles on multiwalled carbon nanotubes, Pd(II)/MWCNT] to carry out N-chelation-directed C-H to C-O, C-Cl, and C-Br transformations is reported. The results presented demonstrate that the solid-supported Pd(II)/MWCNT catalyst can effectively catalyze C-H activation reactions using the Pd(II)/Pd(IV) catalytic cycle.