OPERANDO STUDY OF THE COUPLING REACTIONS USING LIGAND-FREE PALLADIUM CATALYSTS

2016 ◽  
Vol 4 ◽  
pp. 26-36
Author(s):  
Larina E. V. ◽  
◽  
Kurokhtina А. А. ◽  
Yarosh Е. V. ◽  
Lagoda N. А. ◽  
...  
2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Cong Wang ◽  
Hui Zhang ◽  
Lucille A. Wells ◽  
Tian Liu ◽  
Tingting Meng ◽  
...  

AbstractN-Arylation of NH-sulfoximines represents an appealing approach to access N-aryl sulfoximines, but has not been successfully applied to NH-diaryl sulfoximines. Herein, a copper-catalyzed photoredox dehydrogenative Chan-Lam coupling of free diaryl sulfoximines and arylboronic acids is described. This neutral and ligand-free coupling is initiated by ambient light-induced copper-catalyzed single-electron reduction of NH-sulfoximines. This electron transfer route circumvents the sacrificial oxidant employed in traditional Chan-Lam coupling reactions, increasing the environmental friendliness of this process. Instead, dihydrogen gas forms as a byproduct of this reaction. Mechanistic investigations also reveal a unique autocatalysis process. The C–N coupling products, N-arylated sulfoximines, serve as ligands along with NH-sulfoximine to bind to the copper species, generating the photocatalyst. DFT calculations reveal that both the NH-sulfoximine substrate and the N-aryl product can ligate the copper accounting for the observed autocatalysis. Two energetically viable stepwise pathways were located wherein the copper facilitates hydrogen atom abstraction from the NH-sulfoximine and the ethanol solvent to produce dihydrogen. The protocol described herein represents an appealing alternative strategy to the classic oxidative Chan-Lam reaction, allowing greater substrate generality as well as the elimination of byproduct formation from oxidants.


2021 ◽  
Vol 01 ◽  
Author(s):  
Sharwari K. Mengane ◽  
Ronghui Wu ◽  
Liyun Ma ◽  
Chhaya S. Panse ◽  
Shailesh N. Vajekar ◽  
...  

: Catalysis is the multidisciplinary field involving many areas of chemistry, notably in organometallic chemistry and materials science. It has great applications in synthesis of many industrially applicable compounds such as fuels and fine chemicals. The activity and selectivity are a key issue in catalysis that generally allied to high surface area. The current research activities mainly deal with the homogeneous and heterogeneous catalysis. Homogeneous and heterogeneous catalysis have certain drawbacks which restricts their application to great extent but have their own advantages. Hence, it has a predominant concern of current research to find out an alternate to overcome their drawbacks. Therefore, it is highly desirable to find a catalytic protocol that offers high selectivity and excellent product yield with quick and easy recovery. Along with their various applications as alternatives to conventional bulk materials nanomaterial have established its great role in different industrial and scientific applications. Nanocatalysis has emerged as new alternative to the conventional homogeneous and heterogeneous catalysis. The nanomaterials are responsible to enhance surface area of the catalyst, which ultimately increases the catalyst reactants contacts. In addition, it acts as robust material and has high surface area like heterogeneous catalysts. Insolubility of such nanomaterial in reaction medium makes them easily separable, hence, catalyst can be easily separate from the product. Hence, it has been proven that nanocatalysts behave like homogeneous as well as heterogeneous catalysts which work as a bridge between the conventional catalytic systems. Considering these merits; researchers has paid their attention towards applications of nanocatalyst in several organic reactions. This review article focused on the catalytic applications of metal nanoparticles (MNPs) such as Pd, Ag, Au, Cu, Pt in ligand free coupling reactions. In addition, it covers applications of bimetallic and multimetallic nanoparticles in ligand free coupling reactions.


Catalysts ◽  
2019 ◽  
Vol 9 (5) ◽  
pp. 461 ◽  
Author(s):  
Yamada ◽  
Masuda ◽  
Park ◽  
Tachikawa ◽  
Ito ◽  
...  

The catalyst activities of various heterogeneous palladium catalysts supported by anatase-, rutile- and brookite-type titanium oxide for ligand-free Suzuki–Miyaura cross-coupling reactions of aryl chlorides were evaluated. Palladium acetate [Pd(OAc)2], supported on anatase-type titanium oxide (TiO2) via acetonitrile solution impregnation process without reduction [Pd/TiO2 (anatase-type)], demonstrated the highest catalyst activity in comparison to those of other titanium oxide (rutile- or brookite-type) supported Pd(OAc)2 without reduction and reduced Pd/TiO2 (anatase-type) [Pd(red)/TiO2 (anatase-type)]. Various aryl chloride and bromide derivatives were smoothly coupled with arylboronic acids including heteroarylboronic acids in the presence of 5–10 mol% Pd/TiO2 (anatase-type) without the addition of any ligands. Although the fresh Pd/TiO2 (anatase-type) catalyst was surprisingly comprised of ca. 1:2 mixture of palladium(II) and palladium(0) species according to X-ray photoelectron spectroscopy (XPS), in spite of no reduction process, significant further increment of palladium(0) species was observed during the Suzuki–Miyaura coupling reaction, and Pd/TiO2 (anatase-type) was converted into a catalyst, which contained palladium(0) species as the main component [ca. 1:5 mixture of palladium(II) and palladium(0) species]. Therefore, the reduction via the electron donation process to the palladium(II) species may have occurred during the reaction on anatase-type titanium oxide.


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