Reaction Of Alkynes Research Articles

Utilizing perhalopyridine-based alkynes as suitable precursors for the synthesis of novel poly(1,2,3-triazolyl)-substituted perhalopyridines.

A novel series of poly(1,2,3-triazolyl)-substituted perhalopyridines 5a-f were successfully synthesized from the click reaction of the terminal alkynes (drived from the nucleophilic substitution reactions of PFP 1a and PCP 1b with excess amounts of propargyl alcohol) with aryl azides 4a-c under ultrasonic irradiation. Likewise, the sonication of reaction mixtures containing pyridyl cores 3, alkyl bromides 6a,b, and NaN3 under one-pot conditions afforded their respective aliphatic 1,2,3-triazoles 7a-d in yields ranging from 71% to 83%. We next developed an effective method for the regioselective preparation of 2,3,4,5-tetrachloro-6-(prop-2-yn-1-yloxy)pyridine 3c through SNAr reaction of PCP with propargyl alcohol without the utilization of any catalyst. It was then used to fabricate several ((1,2,3-triazol-4-yl)methoxy)-3,4,5,6-tetrachloropyridines 8a-c under the reaction conditions. Finally, the Pd(PPh3)4-catalyzed SMC reaction of tris-triazoles 5b,e with arylboronic acids 9a-c offered a practical method for the synthesis of biaryl-embedded poly(1,2,3-triazoles) 10a-f in good yields.

Recent advances in the applications of gem-difluoromethylene alkynes.

As a special class of alkynes, gem-difluoromethylene alkynes exhibit a variety of fascinating properties due to the presence of the gem-difluoro substitution. This substitution highlights the distinctive fluorine effects in influencing the chemoselectivity of reactions. As a result, chemical scientists have shown great interest and enthusiasm for investigating their reactions. In this review, we briefly summarize recent advances in transition metal-catalysed reactions of gem-difluoromethylene alkynes with multiple reaction pathways. Their mechanistic studies and challenges will be highlighted. The purpose of this review is to provide illustrations of elegant gem-difluoromethylene alkynes and thereby elicit further interest among synthetic chemists in developing innovative transformations of gem-difluoromethylene alkynes.

A highly sensitive and selective fluorescent biosensor for breast cancer derived exosomes using click reaction of azide-CD63 aptamer and alkyne-polymer dots.

Exosomes have gained recognition as valuable reservoirs of biomarkers, holding immense potential for early cancer detection. Consequently, there is a pressing need for the development of an economical and highly sensitive exosome detection methodology. In this work, we present a fluorescence method for breast cancer-derived exosome detection based on Cu-triggered click reaction of azide-modified CD63 aptamer and alkyne functionalized Pdots. The detection threshold for the exosomes obtained from the breast cancer serum was determined to be 6.09 × 107 particles per μL, while the measurable range spanned from 6.50 × 107 to 1.30 × 109 particles per μL. The employed methodology achieved notable success in accurately distinguishing breast cancer patients from healthy individuals through serum analysis. The application of this method showcases the significant potential for early exosome analysis in the clinical diagnosis of breast cancer patients.

Unprecedented Mo3S4 cluster-catalyzed radical C-C cross-coupling reactions of aryl alkynes and acrylates.

A new method for the generation of benzyl radicals from terminal aromatic alkynes has been developed, which allows the direct cross coupling with acrylate derivatives. Our additive-free protocol employs air-stable diamino Mo3S4 cubane-type cluster catalysts in the presence of hydrogen. A sulfur-centered cluster catalysis mechanism for benzyl radical formation is proposed based on catalytic and stoichiometric experiments. The process starts with the cluster hydrogen activation to form a bis(hydrosulfido) [Mo3(μ3-S)(μ-S)(μ-SH)2Cl3(dmen)3]+intermediate. The reaction of various aromatic terminal alkynes containing different functionalities with a series of acrylates affords the corresponding Giese-type radical addition products.

Electrochemical stereoselective synthesis of polysubstituted 1,4-dicarbonyl Z-alkenes via three-component coupling of sulfoxonium ylides and alkynes with water.

The first straightforward strategy for the synthesis of 1,4-dicarbonyl Z-alkenes has been developed via an electrochemical cross-coupling reaction of sulfoxonium ylides and alkynes with water. The metal-free protocol showed an easy-to-handle nature, good functional group tolerance, and high Z-stereoselectivity, which is rare in previous cases. The proposed reaction mechanism was convincingly established by carrying out a series of control experiments, cyclic voltammetry experiments, and density functional theory (DFT) studies.

Silanes as a versatile hydride source for Ni–H catalysis: a promising tool for π-hydro functionalization

Nickel-catalyzed hydrofunctionalization of π-substrates is a possibly effective method to synthesize several value-added molecular architectures. This review covers the NiH catalyzed hydrofunctionalization reactions of alkenes, alkynes and allenes.

Bench-stable Nickel(II)–aryl Complex-Catalyzed cyclotrimerisation of diynes and alkynes to synthesis multisubstituted benzene derivatives

Herein, we report a (PPh3)2Ni(o-tolyl)Cl complex-catalyzed cyclotrimerisation reaction of diynes and alkynes to furnish multi-substituted benzene derivatives in moderate to excellent yields. This method features an air-stable catalyst, green reaction conditions, and excellent functional group tolerance. Additionally, this approach enables gram-scale synthesis, and the target product could also be further derivatised into important isoindolinone scaffolds. These demonstrate the potential application of this methodology.

Zinc amidinate-catalysed cyclization reaction of carbodiimides and alkynes. An insight into the mechanism.

A synthesis of iminopyridines based on zinc has been developed. The commercially available ZnEt2 was employed as a precatalyst for this process. A mechanism has been proposed on the basis of Density Functional Theory (DFT) studies and stoichiometric reactions. The zinc amidinato intermediates underscore the critical role of zinc in this synthesis process.

Palladium-catalyzed synthesis of indene-1-acetates via sequential double carbopalladation and aryloxycarbonylation

A novel palladium-catalyzed cascade reaction of o-iodostyrenes, internal alkynes and formates to access various indene-1-acetates through sequential double carbopalladation and aryloxycarbonylation under a palladium/air system was developed.

Palladium-catalyzed syn-alkynylarylation of internal alkynes: rapid access to all-carbon tetrasubstituted alkenes.

Herein, a straightforward method for rapid access to all-carbon tertrasubstituted alkenes bearing alkyl, aryl and alkynyl groups is established via palladium-catalyzed three-component cross-coupling reaction of internal alkynes, haloalkynes and arylboronic acids. This protocol is characterized by a broad substrate scope and excellent chemo- and regioselectivities. The dual beneficial roles of silver salts in activating haloalkynes and inhibiting bromoalkynylation have been demonstrated by serving as both the Lewis acid and halide scavenger.

Magic effect of diphenylprolinol silyl ether for the enantioselective allenation of 2-alkynals

Chiral diphenylprolinol silyl ethers have been successfully identified for the enantioselective allenation reaction of terminal alkynes and 2-alkynals, delivering a diverse set of chiral allenynes with high efficiency.

Copper-Based Solid Wastes Promoted Cross-Coupling Reactions of Terminal Alkynes

Copper-Based Solid Wastes Promoted Cross-Coupling Reactions of Terminal Alkynes

NiH-catalyzed C-N bond formation: insights and advancements in hydroamination of unsaturated hydrocarbons.

The formation of C-N bonds is a fundamental aspect of organic synthesis, and hydroamination has emerged as a pivotal strategy for the synthesis of essential amine derivatives. In recent years, there has been a surge of interest in metal hydride-catalyzed hydroamination reactions of common alkenes and alkynes. This method avoids the need for stoichiometric organometallic reagents and overcomes problems associated with specific organometallic compounds that may impact functional group compatibility. Notably, recent developments have brought to the forefront olefinic hydroamination and hydroamidation reactions facilitated by nickel hydride (NiH) catalysis. The inclusion of suitable chiral ligands has paved the way for the realization of asymmetric hydroamination reactions in the realm of olefins. This review aims to provide an in-depth exploration of the latest achievements in C-N bond formation through intermolecular hydroamination catalyzed by nickel hydrides. Leveraging this innovative approach, a diverse range of alkene and alkyne substrates can be efficiently transformed into value-added compounds enriched with C-N bonds. The intricacies of C-N bond formation are succinctly elucidated, offering a concise overview of the underlying reaction mechanisms. It is our aspiration that this comprehensive review will stimulate further progress in NiH-catalytic techniques, fine-tune reaction systems, drive innovation in catalyst design, and foster a deeper understanding of the underlying mechanisms.

Photocatalysis as a green alternative toolkit for the construction of nitrogen-enriched heterocycles via the direct and indirect activation of alkynes/alkenes

By harnessing the reactivity of alkynes and alkenes under photochemical conditions, novel pathways have been unlocked to construct N-heterocyclic compounds, allowing for more efficient and sustainable synthesis.

Recent advances in the application of alkynes in multicomponent reactions.

Alkynes have two active positions to carry out chemical reactions: C[triple bond, length as m-dash]C and C-H. These two positions are involved and activated in different reactions using different reagents. In this study, we investigated the reactions of alkynes that are involved in multi-component reactions through the C-C and C-H positions and examined the progress and gaps of each reaction by carefully studying the mechanism of the reactions. Firstly, we investigated and analyzed the reactions involving the C[triple bond, length as m-dash]C position of alkynes, including the reactions between derivatives of alkynes with RN3, sulfur compounds (RSO2R', DMSO, S8, DABCO(SO2)2 and DABSO), barbituric acids, aldehydes and amines, COOH, α-diazoesters or ketones, and isocyanides. Then, we examined and analyzed the important reactions involving the C-H position of alkynes and the progress and gaps in these reactions, including the reaction between alkyne derivatives with amines and aldehydes for the synthesis of propargylamines, the reaction between alkynes with CO2 and the reaction between alkynes with CO.

Highly selective and additive-free Pd(OAc)2/CPP catalyzed hydroaminocarbonylation of alkynes.

Herein, the synthesis of branched α,β-unsaturated amides by a hydroaminocarbonylation reaction of alkynes with various amine substrates such as aromatic amines, aliphatic amines, solid amine sources like NH4HCO3, and even strongly basic piperidines is reported, using a Pd(OAc)2/hybrid N-heterocyclic carbene-phosphine-phosphine (CPP) catalytic system. The reactions feature no additives, wide substrate scope, high selectivity (b/l > 99 : 1) and excellent yields. Mechanistic studies have disclosed that the reaction takes place via a palladium hydride pathway. CPP adopts a hybrid bidentate ligand conformation with a carbene-phosphine coordination mode, wherein one phosphorus atom remains externally accessible, potentially serving as a stabilizing auxiliary during catalytic cycles.

100% selective cyclotrimerization of acetylene to benzene on Ag(111).

Benzene, a high-volume chemical, is produced from larger molecules by inefficient and environmentally harmful processes. Recent changes in hydrocarbon feedstocks from oil to gas motivate research into small molecule upgrading. For example, the cyclotrimerization of acetylene reaction has been demonstrated on Pd, Pd alloy, and Cu surfaces and catalysts, but they are not 100% selective to benzene. We discovered that acetylene can be converted to benzene with 100% selectivity on the Ag(111) surface. Our temperature programmed desorption experiments reveal a threshold acetylene surface coverage of ∼one monolayer, above which benzene is formed. Furthermore, additional layers of acetylene increase the amount of benzene produced while retaining 100% selectivity. Our scanning tunneling microscopy images show that acetylene prefers square packing on the Ag(111) surface at low coverages, which converts to hexagonal packing when acetylene multilayers are present. Within this denser layer, features consistent with the proposed C4 intermediates of the cyclotrimerization process are observed. Density functional theory calculations demonstrate that the barrier for forming the crucial C4 intermediate generally decreases as acetylene multilayers are formed because the multilayer interacts more strongly with the surface in the transition state than in the initial state. Given that acetylene desorbs from Ag(111) at ∼90 K, the C4 intermediate on the pathway to benzene must be formed below this temperature, implying that if Ag-based heterogeneous catalysts can be run at sufficiently high pressure and low enough temperature, efficient and selective trimerization of acetylene to benzene may be possible.

Combining Bayesian optimization and automation to simultaneously optimize reaction conditions and routes

Combining a cloud-based Bayesian optimization platform with a robotic synthesis platform accelerated the discovery of high conversion iodination of terminal alkyne reactions in a large search space of over 12 000 possible reactions in 23 experiments.

Ligand Control of Copper-Mediated Cycloadditions of Acetylene to Azides: Chemo- and Regio-Selective Formation of Deutero- and Iodo-Substituted 1,2,3-Triazoles.

The participation of σ-monocopper and σ-bis-copper acetylide in mechanistic pathways for copper-catalyzed cycloaddition (CuAAC) reactions of acetylene with azides was probed by analysis of deuterium distributions in the 1,2,3-triazole product formed by deuterolysis of initially formed mono- and bis-copper triazoles. The results show that, when Cu(Phen)(PPh3)2NO3 is used as the catalyst for reactions of acetylene with azides in DMF/D2O, 1-substituted-5-deutero-1,2,3-triazoles are generated selectively. This finding demonstrates that the Cu(Phen)(PPh3)2NO3-catalyzed cycloadditions utilize monocopper acetylide as the substrate and produce 5-copper-1,2,3-triazoles initially. Conversely, when DBU or Et3N is the copper ligand, the process takes place through initial formation and cycloaddition of bis-copper acetylide to produce 4,5-bis-copper-triazole, which reacts with D2O to form the corresponding 4,5-bis-deutero-triazole. Moreover, when C2D2 is used as the substrate, Cu(Phen)(PPh3)2NO3 as the Cu ligand, and H2O/DMF as the solvent, mono-C4-deutreo 1,2,3-triazoles are generated in high yields and excellent levels of regioselectivity. Lastly, CuAAC reactions of acetylene with azides, promoted by CuCl2·2H2O and NaI, yield 4,5-diiodo-1,2,3-triazoles with moderate to high efficiencies.

1-Butyl-3-methylimidazolium tetrafluoroborate as suitable solvent for BF3: the case of alkyne hydration. Chemistry vs electrochemistry.

In order to replace the expensive metal/ligand catalysts and classic toxic and volatile solvents, commonly used for the hydration of alkynes, the hydration reaction of alkynes was studied in the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMIm-BF4) adding boron trifluoride diethyl etherate (BF3·Et2O) as catalyst. Different ionic liquids were used, varying the cation or the anion, in order to identify the best one, in terms of both efficiency and reduced costs. The developed method was efficaciously applied to different alkynes, achieving the desired hydration products with good yields. The results obtained using a conventional approach (i.e., adding BF3·Et2O) were compared with those achieved using BF3 electrogenerated in BMIm-BF4, demonstrating the possibility of obtaining the products of alkyne hydration with analogous or improved yields, using less hazardous precursors to generate the reactive species in situ. In particular, for terminal arylalkynes, the electrochemical route proved to be advantageous, yielding preferentially the hydration products vs the aldol condensation products. Importantly, the ability to recycle the ionic liquid in subsequent reactions was successfully demonstrated.