Catalyst For Cross-coupling Research Articles

Upcycling of Chitin to Cross-Coupling Catalysts: Tailored Supports and Opportunities in Mechanochemistry.

In this study chitin derived from shrimp shells was used in the design of heterogeneous Pd-based catalysts for Heck and Suzuki-Miyaura cross-coupling reactions. The synthesis of Pd nanoparticles supported on N-doped carbons was performed through different approaches, including a sustainable mechanochemical approach, by using a twin-screw extruder. All catalytic systems were characterized by a multitechnique approach and the effect of nanoparticles size, N-doping on the support, and their synergistic interactions were elucidated. Specifically, Kelvin Probe Atomic Force Microscopy provided valuable insights on charge transfer and metal-support interactions. The catalytic behaviour of the samples was investigated in cross-coupling reactions under batch conditions and under semi-continuous flow solvent-free conditions, respectively obtaining a quantitative yield and a noteworthy productivity of 8.7 mol/(gPdh).

RhRu Bimetallic Cluster Catalysts for Dehydrogenative Cross-Coupling of Arenes and Carboxylic Acids

RhRu Bimetallic Cluster Catalysts for Dehydrogenative Cross-Coupling of Arenes and Carboxylic Acids

A convenient bottom up route to covalently anchor Pd(II)-PEPPSI on layered zirconium(IV) phosphonate: Efficient catalyst for Suzuki-Miyaura cross coupling of aryl chlorides

A rational and bottom-up route for assembling layered Zr(IV) phosphonate framework decorated with covalently anchored N-heterocyclic carbene NHC-Pd(II) fragment has been developed. Reaction of phosphonic acid functionalized Pd(II)-NHC precursor complex with ZrOCl2·8H2O provides easy access to a layered material with covalently anchored catalytically active Pd(II)-NHC sites. The Pd(II)-NHC functionalized Zr(IV) phosphonate showed enhanced catalytic activity in Suzuki-Miyaura cross coupling reaction of both aryl bromides and chlorides with aryl boronic acid, as compared to their homogeneous counterparts. The Zr(IV) phosphonate framework imparts remarkable robustness to the Pd(II)-NHC catalyst and allowed recycling of the catalyst up to nine catalytic cycles without any major loss of catalytic activity.

Immobilization of laccase on mesoporous metal organic frameworks for efficient cross-coupling of ethyl ferulate.

Laccases act as green catalysts for oxidative cross-coupling of phenolic antioxidnt compounds, but low stability and non-recyclability limit its application. To address that, metal-organic frameworks Cu-BTC and Cr-MOF were synthesized as supports to immobilize the efficient laccase from Cerrena sp. HYB07. The Brunauer-Emmett-Teller surface area of Cu-BTC and Cr-MOF were 1213.2 and 907.1m2/g, respectively. The two carriers respectively presented pore diameters of 1.2-10nm and 1.4-12nm as octahedron, indicating nano-scale mesoporosity. These Cu-BTC and Cr-MOF carriers could adsorb laccase with enzyme loading of 1933.2 and 1564.4U/g carrier, respectively. The stability and organic solvent tolerance of Cu-BTC-laccase and Cr-MOF-laccase were both obviously improved compared to free laccase. Thermal inactivation kinetics showed that both the two immobilized laccases displayed lower thermal inactivation rate constants. Importantly, the Cu-BTC-laccase and Cr-MOF-laccase both showed much higher activity for cross-coupling of ethyl ferulate than free laccase, which had 2.5-fold higher cross-coupling efficiency than that by free laccase. The ethyl ferulate coupling product was also analyzed by mass spectroscopy and the synthesis pathway of ethyl ferulate dimer was proposed. The cross coupling of ethyl ferulate required the formation of radical intermediates of ethyl ferulate generated by laccase mediated oxidation. This work paved the way for MOFs immobilized laccase for cross coupling of antioxidant phenols.

Elucidating the Impact of Rare Earth or Transition Metal Identity on the Physical and Electronic Structural Properties of a Series of Redox-Active Tris(amido) Complexes.

The use of redox-active ligands with the f-block elements has been employed to promote unique chemical transformations and explore their unique emergent electronic properties for a myriad of applications. In this study, we report eight new tris(amido) metal complexes: 1-Ln (Ln = Tb3+, Dy3+, Ho3+, Er3+, Tm3+, and Yb3+), 1-La, and 1-Ti (an early transition metal analogue). The one-electron oxidation of the tris(amido) ligand was conducted to generate semi-iminato complexes 2-Ln, 2-La, and 2-Ti, and these complexes were studied using EPR. Tris(amido) complexes 1-Ln, 1-La, and 1-Ti were fully characterized using a range of spectroscopic (NMR and UV-vis/NIR) and physical techniques (X-ray diffraction and cyclic voltammetry, with the exception of 1-La). Computational methods were employed to further elucidate the electronic structures of these complexes. Lastly, complexes 1-Ln, 1-La, and 1-Ti were probed as catalysts for alkyl-alkyl cross-coupling, and the initial rate of the reaction was measured to explore the influence of the metal ion.

Coupling of Aryl Chlorides with Lithium Nucleophiles Enabled by Molecularly Defined Alkynyllithium Palladium Catalysts.

Palladium-catalyzed cross-couplings of aryl chlorides usually call for bulky, electron-rich ligands such as phosphines or heterocyclic carbenes. We have now found that similarly powerful cross-coupling catalysts are obtained by the reaction of palladium salts with alkynyllithium reagents. The species initially formed in this process was characterized as a dilithium tetraalkinyl palladate complex. It catalyzes the coupling of aryl chlorides with the lithium salts of various terminal alkynes to give alkynyl arenes. The isolated Li-alkynyl-Pd complex also efficiently promotes the reaction of aryl, and allyl chlorides with (hetero)aryl-, alkyl-, and allyllithium compounds as well as lithium amides. None of these reactions proceeded in the presence of palladium salts alone. The preparative utility of this approach was demonstrated by the synthesis of 49 molecules, including pharmaceutically relevant compounds.

URJC-1: Stable and Efficient Catalyst for O-Arylation Cross-Coupling.

The design of metal-organic frameworks (MOFs) allows the definition of properties for their final application in small-scale heterogeneous catalysis. Incorporating various catalytic centers within a single structure can produce a synergistic effect, which is particularly intriguing for cross-coupling reactions. The URJC-1 material exhibits catalytic duality: the metal centers act as Lewis acid centers, while the nitrogen atoms of the organic ligand must behave as basic centers. The impact of reaction temperature, catalyst concentration, and basic agent concentration was evaluated. Several copper-based catalysts, including homogeneous and heterogeneous MOF catalysts with and without the presence of nitrogen atoms in the organic ligand, were assessed for their catalytic effect under optimal conditions. Among the catalysts tested, URJC-1 exhibited the highest catalytic activity, achieving complete conversion of 4-nitrobenzaldehyde with only 3% mol copper concentration in one hour. Furthermore, URJC-1 maintained its crystalline structure even after five reaction cycles, demonstrating remarkable stability in the reaction medium. The study also examined the impact of various substituents of the substrate alcohol on the reaction using URJC-1. The results showed that the reaction had high activity when activating substituents were present and for most cyclic alcohols rather than linear ones.

Simple thiazole-based ligands for palladium(II) Suzuki-Miyaura aryl cross-coupling catalysts

Two new palladium(II) catalysts, each containing a phenylthiazole ligand (2-methyl- (1a) and 2-amino-4-phenyl-1,3-thiazole (1b)) are prepared and characterized. The crystal structure of one, 2-methyl-4-phenyl)palladium(II) acetate (3a), is presented; it crystallizes as a dimer, with the ligand attached through the nitrogen on the thiazole and the ortho-carbon on the phenyl ring. The organometallic compounds can be used as catalysts in Suzuki-Miyaura aryl cross-coupling reactions. They are compatible with a wide range of functional groups, including carbonyls, amines, and phenols.

Gold(I) Complex with a Photoactive Ligand Behaves as a Two-in-One Dual Metallaphotoredox Cross-Coupling Catalyst

Gold(I) Complex with a Photoactive Ligand Behaves as a Two-in-One Dual Metallaphotoredox Cross-Coupling Catalyst

Light Activation and Photophysics of a Structurally Constrained Nickel(II)-Bipyridine Aryl Halide Complex.

Transition-metal photoredox catalysis has transformed organic synthesis by harnessing light to construct complex molecules. Nickel(II)-bipyridine (bpy) aryl halide complexes are a significant class of cross-coupling catalysts that can be activated via direct light excitation. This study investigates the effects of molecular structure on the photophysics of these catalysts by considering an underexplored, structurally constrained Ni(II)-bpy aryl halide complex in which the aryl and bpy ligands are covalently tethered alongside traditional unconstrained complexes. Intriguingly, the tethered complex is photochemically stable but features a reversible Ni(II)-C(aryl) ⇄ [Ni(I)···C(aryl)•] equilibrium upon direct photoexcitation. When an electrophile is introduced during photoirradiation, we demonstrate a preference for photodissociation over recombination, rendering the parent Ni(II) complex a stable source of a reactive Ni(I) intermediate. Here, we characterize the reversible photochemical behavior of the tethered complex by kinetic analyses, quantum chemical calculations, and ultrafast transient absorption spectroscopy. Comparison to the previously characterized Ni(II)-bpy aryl halide complex indicates that the structural constraints considered here dramatically influence the excited state relaxation pathway and provide insight into the characteristics of excited-state Ni(II)-C bond homolysis and aryl radical reassociation dynamics. This study enriches the understanding of molecular structure effects in photoredox catalysis and offers new possibilities for designing customized photoactive catalysts for precise organic synthesis.

Cu-SSZ-39 zeolite nanosheets-heterogeneous catalyst for the decarboxylative cross-coupling of cinnamic acids with ethers

Zeolite with nanoscale in some dimensions always display better catalytic performance because it contains more exposed catalytic active sites. Herein, a Cu2+ exchanged SSZ-39 zeolite with nanosheet morphology was chosen as a catalyst for the preparation of 2-vinyl heterocycle ethers through decarboxylative cross-coupling of cinnamic acids with ethers. The template reaction conditions were optimized, and the possible reaction mechanism was proposed. Then, a wide range of 2-vinyl heterocycle ethers were prepared. The recycling experiment demonstrated the good sustainability of the catalyst. The potential value of the catalytic product was demonstrated through the bifunctional addition and hydrogenation reduction.

Alkene Hydrobenzylation by a Single Catalyst That Mediates Iterative Outer-Sphere Steps.

Cross-coupling catalysts typically react and unite functionally distinct partners via sequential inner-sphere elementary steps: coordination, migratory insertion, reductive elimination, etc. Here, we report a single catalyst that cross-couples styrenes and benzyl bromides via iterative outer-sphere steps: metal-ligand-carbon interactions. Each partner forms a stabilized radical intermediate, yet heterocoupled products predominate. The system is redox-neutral and, thus, avoids exogenous oxidants, resulting in simple and scalable conditions. Numerous variations of alkene hydrobenzylation are made possible, including access to the privileged heterodibenzyl (1,2-diarylethane) motif and challenging quaternary carbon variants.

Nickel-catalyzed selective disulfide formation by reductive cross-coupling of thiosulfonates.

Developing innovative methodologies for disulfide preparation is of importance in contemporary organic chemistry. Despite significant advancements in nickel-catalyzed reductive cross-coupling reactions for forming carbon-carbon and carbon-heteroatom bonds, the synthesis of S-S bonds remains a considerable challenge. In this context, we present a novel approach utilizing nickel catalysts for the reductive cross-coupling of thiosulfonates. This method operates under mild conditions, offering a convenient and efficient pathway to synthesize a wide range of both symmetrical and unsymmetrical disulfides from readily available, bench-stable thiosulfonates with exceptional selectivity. Notably, this approach is highly versatile, allowing for the late-stage modification of pharmaceuticals and the preparation of various targeted compounds. A comprehensive mechanistic investigation has been conducted to substantiate the proposed hypothesis.

A redox switchable ferrocene decorated n-heterocyclic carbene (NHC) palladium catalyst for cross coupling of arylboronic acid and acetic anhydride in phosphine, base and additive free conditions

A phosphine, base and additive free cross-coupling of arylboronic acid is reported via C–O bond cleavage of acetic anhydride using a switchable ferrocene functionalized n-heterocyclic carbene (NHC) palladium complex.

Catalyst Deactivation of a Monoligated CyJohnPhos-bound Nickel(0) Complex.

Cross-coupling catalysts are prone to unproductive side reactivity that can limit their practical use in synthetic chemistry. A detailed understanding of these pathways and the conditions that enable them is important for reaction optimization and rational catalyst design. In this work, we report the off-cycle reactivity of a monoligated, CyJohnPhos-bound Ni0 complex following product-forming reductive elimination. In the absence of substrate, free phosphine ligand, or π-accepting additives, dimerization of (CyJohnPhos)Ni0 occurs, followed by C-P bond activation of the ligand to form a phosphido-bridged Ni0/NiII dimer; both the Ni0/Ni0 and Ni0/NiII dimers were structurally characterized. Monomeric (CyJohnPhos)Ni0 must be intercepted by substrate or free ligand to prevent irreversible dimerization and catalyst deactivation.

Mechanochemical Synthesis of PdO2 Nanoparticles Immobilized over Silica Gel for Catalytic Suzuki-Miyaura Cross-Coupling Reactions Leading to the C-3 Modification of 1H-Indazole with Phenylboronic Acids.

The C-3 modification of 1H-indazole has produced active pharmaceuticals for the treatment of cancer and HIV. But, so far, this transformation has seemed less available, due to the lack of efficient C-C bond formation at the less reactive C-3 position. In this work, a series of silica gel-supported PdO2 nanoparticles of 25-66 nm size were prepared by ball milling silica gel with divalent palladium precursors, and then employed as catalysts for the Suzuki-Miyaura cross-coupling of 1H-indazole derivative with phenylboronic acid. All the synthesized catalysts showed much higher cross-coupling yields than their palladium precursors, and could also be reused three times without losing high activity and selectivity in a toluene/water/ethanol mixed solvent. Although the palladium precursors showed an order of activity of PdCl2(dppf, 1,1'-bis(diphenylphosphino)ferrocene) > PdCl2(dtbpf, 1,1'-bis(di-tert-butylphosphino)ferrocene) > Pd(OAc, acetate)2, the synthesized catalysts showed an order of C1 (from Pd(OAc)2) > C3 (from PdCl2(dtbpf)) > C2 (from PdCl2(dppf)), which conformed to the orders of BET (Brunauer-Emmett-Teller) surface areas and acidities of these catalysts. Notably, the most inexpensive Pd(OAc)2 can be used as a palladium precursor for the synthesis of the best catalyst through simple ball milling. This work provides a highly active and inexpensive series of catalysts for C-3 modification of 1H-indazole, which are significant for the large-scale production of 1H-indazole-based pharmaceuticals.

Photoinduced Copper-Catalyzed Enantioconvergent Remote Alkynylation via 1,4-Heteroaryl Migration.

A photoinduced copper-catalyzed enantioconvergent remote alkynylation of N-hydroxyphthalimide esters with terminal alkynes via 1,4-heteroaryl migration has been developed. A broad scope of heteroaryl-tethered chiral alkynes has been synthesized with good regio- and enantioselectivities. The chiral-ligand-coordinated copper species plays a dual role as both the photoredox and cross-coupling catalyst. This methodology provides a new platform for enantioconvergent remote alkynylations.

Carbonyl-Supported Coordination in Imidazolates: A Platform for Designing Porous Nickel-Based ZIFs as Heterogeneous Catalysts.

Zeolitic imidazolate frameworks (ZIFs) are a subclass of metal-organic framework that have attracted considerable attention as potential functional materials due to their high chemical stability and ease of synthesis. ZIFs are usually composed of zinc ions coordinated with imidazole linkers, with some other transition metals, such as Cu(II) and Co(II), also showing potential as ZIF-forming cations. Despite the importance of nickel in catalysis, no Ni-based ZIF with permanent porosity is yet reported. It is found that the presence and arrangement of the carbonyl functional groups on the imidazole linker play a crucial role in completing the preferred octahedral coordination of nickel, revealing a promising platform for the rational design of Ni-based ZIFs for a wide range of catalytic applications. Herein, the synthesis of the first Ni-based ZIFs is reported and their high potential as heterogeneous catalysts for Suzuki-Miyaura cross-coupling C─C bond forming reactions is demonstrated.

Hierarchical NiZn Solid Solution as a Highly Efficient Palladium Free Heterogeneous Catalyst for Suzuki-Miyaura Cross-Coupling Reaction.

In this report, surfactant free solid solution of NiZn with a hierarchical architecture was synthesized via a one-pot colloidal approach. Evidence supporting hierarchical crystal growth and alloying of metals at the atomic level was obtained from field emission scanning electron microscopy and transmission electron microscopy-energy-dispersive X-ray data. Lattice sites of face-centered metallic Ni were found to be occupied by Zn as evident from powder X-ray diffraction where a gradual shift in the peak position and increase in the average lattice parameter upon reduction of the Ni content in the alloy samples can be observed. This well-alloyed, magnetically separable, non-noble metal-based solid solution has the potential to replace the palladium-based catalyst in the Suzuki-Miyaura cross-coupling of aryl halides (-Cl/-Br) and phenylboronic acid. The nanostructured catalyst was formed through the assembly of a triangular spiked and sheet-like structure and is magnetically well separable that is stable enough under the catalytic reaction condition. The developed heterogeneous catalyst and the designed economical catalytic model are the first ever reported work. The catalytic results outperformed most of the reported state-of-the-art works involving the transition metal-based catalyst.

Electronic Structures of Nickel(II)-Bis(indanyloxazoline)-dihalide Catalysts: Understanding Ligand Field Contributions That Promote C(sp2)-C(sp3) Cross-Coupling.

NiII(IB) dihalide [IB = (3aR,3a'R,8aS,8a'S)-2,2'-(cyclopropane-1,1-diyl)bis(3a,8a-dihydro-8H-indeno[1,2-d]-oxazole)] complexes are representative of a growing class of first-row transition-metal catalysts for the enantioselective reductive cross-coupling of C(sp2) and C(sp3) electrophiles. Recent mechanistic studies highlight the complexity of these ground-state cross-couplings but also illuminate new reactivity pathways stemming from one-electron redox and their significant sensitivities to reaction conditions. For the first time, a diverse array of spectroscopic methods coupled to electrochemistry have been applied to NiII-based precatalysts to evaluate specific ligand field effects governing key Ni-based redox potentials. We also experimentally demonstrate DMA solvent coordination to catalytically relevant Ni complexes. Coordination is shown to favorably influence key redox-based reaction steps and prevent other deleterious Ni-based equilibria. Combined with electronic structure calculations, we further provide a direct correlation between reaction intermediate frontier molecular orbital energies and cross-coupling yields. Considerations developed herein demonstrate the use of synergic spectroscopic and electrochemical methods to provide concepts for catalyst ligand design and rationalization of reaction condition optimization.