Coupling Of Alkynes Research Articles

Generation of Bis(pentafluorophenyl)boron Enolates from Alkynes and Their Catalyst‐Free Alkyne Coupling

Carbon‐carbon bond forming reactions are powerful synthetic tools for constructing organic molecular frameworks. In this study, strongly Lewis acidic bis(pentafluorophenyl)boron enolates were generated from alkynes through oxygen transfer from 2,6‐dibromopyridine N‐oxide using tris(pentafluorophenyl)borane [B(C6F5)3]. Boron enolates were highly reactive owing to the strong acidity of the boron centers, and thus immediately coupled with alkynes. N‐Ethynylphthalimide reacted as an alkyne with 2,6‐dibromopyridine N‐oxide and B(C6F5)3 to form a semi‐stable bis(pentafluorophenyl)boron enolate through the coordination of the carbonyl group to the boron center. This enolate underwent coupling with another alkyne.

Generation of Bis(pentafluorophenyl)boron Enolates from Alkynes and TheirCatalyst-Free Alkyne Coupling.

Carbon-carbon bond forming reactions are powerful synthetic tools for constructing organic molecular frameworks. In this study, strongly Lewis acidic bis(pentafluorophenyl)boron enolates were generated from alkynes through oxygen transfer from 2,6-dibromopyridine N-oxide using tris(pentafluorophenyl)borane [B(C6F5)3]. Boron enolates were highly reactive owing to the strong acidity of the boron centers, and thus immediately coupled with alkynes. N-Ethynylphthalimide reacted as an alkyne with 2,6-dibromopyridine N-oxide and B(C6F5)3 to form a semi-stable bis(pentafluorophenyl)boron enolate through the coordination of the carbonyl group to the boron center. This enolate underwent coupling with another alkyne.

Copper Catalysts Anchored on Cysteine-Functionalized Polydopamine-Coated Magnetite Particles: A Versatile Platform for Enhanced Coupling Reactions

Cysteine plays a crucial role in the development of an efficient copper-catalyst system, where its thiol group serves as a strong anchoring site for metal coordination. By immobilizing copper onto cysteine-modified, polydopamine-coated magnetite particles, this advanced catalytic platform exhibits exceptional stability and catalytic activity. Chemical modification of the polydopamine (PDA) surface with cysteine enhances copper salt immobilization, leading to the formation of the Fe3O4@PDA-Cys@Cu platform. This system was evaluated in palladium-free, copper-catalyzed Sonogashira coupling reactions, effectively catalyzing the coupling of terminal acetylenes with aryl halides. Additionally, the Fe3O4@PDA-Cys@Cu platform was employed in click reactions, confirming the enhanced catalytic efficiency due to increased copper content. The reusability of the platform was further investigated, demonstrating improved performance, especially in recyclability tests in click reaction, making it a promising candidate for sustainable heterogeneous catalysis.

AgOTf-catalyzed three-component coupling for the synthesis of C-alkynyl iminosugars

A3 coupling of tosylribose, primary amine and alkyne has been accomplished for the synthesis of C-alkynyl iminosugars using a catalytic amount of AgOTf under extremely mild conditions. This method is compatible with acid sensitive acetonide and cyclohexylidene and also TBS and PMB ethers The reaction proceeds through a cyclic iminium ion, which is formed from tosylribose and a primary amine followed by the attack of alkyne resulting in the formation of C-alkynyl iminosugar, which is a key intermediate of many biologically important natural products.

Rhodium Catalysts Based on Phenyl Substituted Cp Ligands for Indole Synthesis via Oxidative Coupling of Acetanilides and Alkynes

AbstractRhodium‐catalyzed oxidative coupling of acetanilides and alkynes via C−H activation is the most powerful synthetic tool for producing the indole motif from commercially available precursors. However, this reaction usually requires large catalyst loadings (5 mol% of rhodium). In this study, a 1,2‐diphenylcyclopentadienyl ligand‐based catalyst was developed that works well at 1 mol% loading of rhodium. DFT calculations of the C−H activation step provided insight into its high catalytic activity. The catalyst efficiency was also demonstrated in the synthesis of naturally occurring isocoumarins, such as polygonolide, tubakialactone B and penicimarine F. The developed catalytic protocols tolerate a wide range of functional groups, for example, halide, nitro, hydroxy, and alkoxy.

Copper on charcoal: copper nanoparticles catalyzed for highly efficient aerobic oxidative coupling of terminal alkynes

Copper on charcoal: copper nanoparticles catalyzed for highly efficient aerobic oxidative coupling of terminal alkynes

Synergistic Homogeneous Asymmetric Cu Catalysis with Pd Nanoparticle Catalysis in Stereoselective Coupling of Alkynes with Aldimine Esters.

Understanding the nature of a transition-metal-catalyzed process, including catalyst evolution and the real active species, is rather challenging yet of great importance for the rational design and development of novel catalysts, and this is even more difficult for a bimetallic catalytic system. Pd(0)/carboxylic acid combined system-catalyzed allylic alkylation reaction of alkynes has been used as an atom-economical protocol for the synthesis of allylic products. However, the asymmetric version of this reaction is still rather limited, and the in-depth understanding of the nature of active Pd species is still elusive. Herein we report an enantioselective coupling between readily available aldimine esters and alkynes using a synergistic Cu/Pd catalyst system, affording a diverse set of α-quaternary allyl amino ester derivatives in good yields with excellent enantioselectivities. Mechanistic studies indicated that it is most likely a synergistic asymmetric molecular Cu catalysis with Pd nanoparticle catalysis. The Pd catalyst precursor is transformed to soluble Pd nanoparticles in situ, which are responsible for activating the alkyne to an electrophilic allylic Pd intermediate, while the chiral Cu complex of the aldimine ester enolate provides chiral induction and works in synergy with the Pd nanoparticles.

Insights Into the Magnesium‐Catalyzed Catalyzed C‐C Coupling of Terminal Alkynes with Carbodiimides.

Insights Into the Magnesium‐Catalyzed Catalyzed C‐C Coupling of Terminal Alkynes with Carbodiimides.

Regiocontrollable B(2/3)-H Alkenylation of nido-Carboranes.

Anionic nido-carboranes, as open-cage analogues of closo-carboranes with strong hydrophilicity and higher potential in the development of biomedicines, have been notably more challenging because of their strong interaction with transition metals. While the exo-cage B-H activation reactions of nido-carboranes have been widely studied, there are few reports on the direct functionalization of B-H bonds located on a closed polyhedral sphere. Here, we report an efficient palladium-catalyzed regioselective B(2/3)-H alkenylation of nido-carboranes with various alkenes and alkyne coupling partners, enabled by 3-methylpyridine directing groups, to achieve a regiocontrollable functionalization of B(2/3)-H vertices over highly reactive exo-cage B11-H vertex in nido-carboranes.

TBHP Promotes Cross-Dehydrogenative Coupling of SF4 Alkynes with Tetrahydroisoquinolines under Copper Catalysis.

We present a viable approach for the cross-dehydrogenative coupling of Het-SF4-alkynes with tetrahydroisoquinolines under oxidative conditions, using TBHP and copper catalysts. These newly developed conditions boast enhanced yields and a more extensive range of substrates, demonstrating tolerance to various functional groups and addressing the limitations of earlier reports. Consequently, this method should increase opportunities for the exploration of SF4-containing compounds and their potential applications in drug discovery, materials science, and as alternatives to PFAS.

Water-catalyzed iron-molybdenum carbyne formation in bimetallic acetylene transformation

Transition metal carbyne complexes are of fundamental importance in carbon-carbon bond formation, alkyne metathesis, and alkyne coupling reactions. Most reported iron carbyne complexes are stabilized by incorporating heteroatoms. Here we show the synthesis of bioinspired FeMo heterobimetallic carbyne complexes by the conversion of C2H2 through a diverse series of intermediates. Key reactions discovered include the reduction of a μ-η2:η2-C2H2 ligand with a hydride to produce a vinyl ligand (μ-η1:η2-CH = CH2), tautomerization of the vinyl ligand to a carbyne (μ-CCH3), and protonation of either the vinyl or the carbyne compound to form a hydrido carbyne heterobimetallic complex. Mechanistic studies unveil the pivotal role of H2O as a proton shuttle, facilitating the proton transfer that converts the vinyl group to a bridging carbyne.

Photo-catalyzed dearomative coupling of benzylmalonates and alkynes with CO2 leading to spiro-1,4-cyclohexadiene carboxylic acids

A dearomative coupling reaction of benzylmalonates and alkynes with CO2via visible-light catalysis is developed, leading to a series of spiro-1,4-cyclohexadiene carboxylic acids. This three-component transformation achieves sequential dearomatization, alkenylation, and carboxylation of non-activated bezene ring, building spiro architecture and installing two functional groups in one reaction step. The strategy has the advantages of mild conditions, broad substrate scope, low loading of photocatalyst, redox neutral, excellent yield and high selectivity. Gram-scale reaction and product derivatizations indicate promising application prospects. Mechanistic studies reveal that the reaction might proceed through tandem radical addition, dearomatization and nucleophilic addition.

Cobalt‐Catalyzed Regioselective Methylative Coupling of Internal Alkynes with Aldehydes/Aldimines

Cobalt‐Catalyzed Regioselective Methylative Coupling of Internal Alkynes with Aldehydes/Aldimines

Design of efficient benzimidazole-derived N-heterocyclic carbene Ag(I) catalysts for aldehyde–amine–alkyne coupling

A mild catalytic protocol for aldehyde, amine, and alkyne coupling (A3-coupling) allows for the selective synthesis of propargyl amines using 5,6-dimethylbenzimidazole-derived N-heterocyclic carbene (BNHC) silver(I) catalysts. A series of BNHC Ag(Ⅰ) halide complexes were synthesized and their structures have been elucidated through the use of multinuclear NMR and FT-IR spectroscopy. Furthermore, the pseudo-linear geometry of two different compounds was substantiated by single-crystal X-ray diffraction. Silver-based A3-coupling was achieved for both acyclic and cyclic secondary amines using a diverse set of alkynes to afford propargyl amines with yields of up to 95 %. The present approach is environmentally benign and water is generated as the sole byproduct.

Nickel-Catalyzed Multicomponent Assembly of Alkynes toward α-CF3-Alkenes.

We disclose an efficient nickel catalytic system for expediting the coupling of alkynes with fluoroalkyl hydrazones and boronic acids, thus facilitating the synthesis of stereospecific α-fluoroalkyl-alkene derivatives. 3H-Pyrazoles might be involved as key intermediates through a nitrogen-releasing process, enabling subsequent coupling with boronic acids to afford 1,2-difunctional alkenes in a highly efficient and step-economical fashion. This tandem platform demonstrates broad functional group tolerance, including complex natural products and drug-like molecules.

Aminocarbyne-Alkyne Coupling in Diruthenium Complexes: Exploring the Anticancer Potential of the Resulting Vinyliminium Complexes and Comparison with Diiron Homologues.

New diruthenium complexes based on the scaffold Ru2Cp2(CO)2 (Cp = η5-C5H5) and containing a bridging vinyliminium ligand, [2a-d]CF3SO3, were synthesized through regioselective coupling of alkynes with an aminocarbyne precursor (85-90% yields). The reaction involving phenylacetylene proceeded with the formation of a diruthenacyclobutene byproduct, [4]CF3SO3 (10% yield). Complexes [2a-d]+ undergo partial alkyne extrusion in contact with alumina or CDCl3. All products were characterized by elemental analysis, infrared and multinuclear NMR spectroscopy, and single crystal X-ray diffraction in two cases. Complexes [2a-d]+ revealed an outstanding stability in DMEM cell culture medium at 37 °C (<1% degradation over 72 h). These complexes exhibited cytotoxicity in human colon colorectal adenocarcinoma HT-29 cells in the low micromolar range, with lower IC50 values than those obtained with the homologous diiron complexes previously reported. Evaluation of ROS (reactive oxygen species) production and O2 consumption rate (OCR) highlighted the higher potential of Ru2 complexes, compared to the Fe2 counterparts, to impact mitochondrial activity, with the heterometallic Ru2-ferrocenyl complex [2d]+ showing the best performance.

Sustainable sonochemical synthesis of N‐protected piperazine‐propargylamines using ionic liquids and CuI

We present a simple method to prepare diverse benzimidazolium and imidazolium ionic liquids (ILs) from common starting materials imidazole and benzimidazole. These green ILs promote the synthesis of N‐substituted piperazinyl propargylamines via a versatile CuI‐catalyzed coupling of aldehydes, secondary amines, and alkynes under ultrasound. Remarkably, the method works across a broad range of substrates, including diversely substituted aldehydes, heterocycles, cyclic amines, and phenylacetylenes. To understand this versatility, we investigated the influence of IL structure (N‐substitution, anion) on reactivity. Symmetrical long‐chain substituents on the benzimidazolium cation and bromide (Br−) anions led to the most efficient propargylamine formation. This approach offers a sustainable and efficient route to propargylamines with minimal waste and catalyst/IL recyclability over five cycles.

The Inorganic Ligand‐Supported Copper Catalyst Catalyzing Alkyne Coupling Reactions

AbstractGlaser‐coupled synthesized 1,3‐diyne can participate in the generation of conjugated polymers and is now widely used in organic and polymer synthesis. Currently, the catalyst in coupling are mostly based on the complexation of noble metals with complex organic ligands, which inevitably increases the research cost and storage difficulty. However, polyoxometalates (POMs), with acidic and redox properties, can be used as an excellent inorganic ligands with low cost and easy storage. In this work, we have synthesized copper catalyst 1, (NH4)4[CuMo6O18(OH)6] with polyoxometalates as inorganic ligands in a facile way and applied them in the coupling of alkynes to obtain (non)symmetrical conjugated 1,3‐diynes in high yields without bases, finally proposing a reasonable reaction path. In addition, the catalyst showed good tolerance to a variety of different groups, further demonstrating its excellent catalytic activity. It is worth mentioning that the catalyst maintained its good structure and activity after six cycles, demonstrating its promising potential for industrial applications. Thus, this paper provides a new strategy for the preparation of (un)symmetrical diynes using polyoxometalates of Cu as catalyst, and also demonstrates the potential of multi‐acid catalyst for organocatalytic applications.

Intermolecular Allene–Alkyne Coupling: A Significantly Useful Synthetic Transformation

Intermolecular Allene–Alkyne Coupling: A Significantly Useful Synthetic Transformation

N‐Heterocyclic Olefin‐Phosphines Based Cationic Ruthenium Complexes as Pre‐Catalysts for Dual C−H Bond Functionalizations

AbstractTwo N‐heterocyclic olefin‐phosphines (NHOP), and the corresponding ruthenium complexes were synthesized and structurally characterized. One of the cationic complexes [(BzIM)(NHOP)Ru(p‐cymene)Cl2]I was employed as a catalyst in N‐benzylbenzamides/alkyne coupling reactions. With this catalytic protocol a variety of substituted isoquinolones were synthesized through ortho‐selective double C−H bond functionalization involving oxidative annulation followed by olefination reactions. All these products were achieved in one‐pot manner without the use of additives.