49824-05-7

Upstream product

• 766-96-1 4-bromo-1-ethynylbenzene 
• 2063-19-6 4-bromo-2-methylbut-3-yn-2-ol 
• 115-19-5 2-methyl-but-3-yn-2-ol 

Downstream Products

• 60214-13-3 1-bromo-4-(1,3-butadiyn-1-yl)benzene 

Relevant academic research and scientific papers

Palladium supported on amine-functionalized mesoporous silica: Highly efficient phosphine-free catalyst for alkyne-alkyne cross-coupling reaction

An amine-functionalized mesoporous silica SBA-15 supported palladium catalyst was prepared and characterized. For the first time, this supported palladium has been used as an efficient phosphine-free and reusable catalyst for the cross-coupling of haloalkynes with terminal alkynes. A variety of haloalkynes and aromatic/aliphatic terminal alkynes were selectively coupled to afford unsymmetrical 1,4-disubstituted 1,3-diynes in good yields.

In Situ Synthesis of CuN4/Mesoporous N-Doped Carbon for Selective Oxidative Crosscoupling of Terminal Alkynes under Mild Conditions

The 1,3-conjugated diynes are an important class of chemical intermediates, and the selective crosscoupling of terminal alkynes is an efficient chemical process for manufacturing asymmetrical 1,3-conjugated diynes. However, it often occurs in homogenous conditions and costs a lot for reaction treatment. Herein, a copper catalyzed strategy is used to synthesize highly ordered mesoporous nitrogen-doped carbon material (OMNC), and the copper species is in situ transformed into the copper single-atom site with four nitrogen coordination (CuN4). These features make the CuN4/OMNC catalyst efficient for selective oxidative crosscoupling of terminal alkynes, and a wide range of asymmetrical and symmetrical 1,3-diynes (26 examples) under mild conditions (40?°C) and low substrates ratio (1.3). Density functional theory (DFT) calculations reveal that the aryl–alkyl crosscoupling has the lowest energy barrier on the CuN4 site, which can explain the high selectivity. In addition, the catalyst can be separated and reused by simply centrifugation or filtration. This work can open a facile avenue for constructing single-atom loaded mesoporous materials to bridge homogeneous and heterogeneous catalysis.

Tuning of cross-Glaser products mediated by substrate-catalyst polymeric backbone interactions

Tuning of cross-Glaser products using different polymeric backbones supported by copper oxide nano-catalysts has been demonstrated by tweaking the substrate-catalyst interactions under greener conditions. Further, highly reactive magnetically separable and recyclable catalyst with scalability is demonstrated.

Copper Nanoparticles on Ordered Mesoporous Carbon Nitride Support: a Superior Catalyst for Homo- and Cross-Coupling of Terminal Alkynes under Base-Free Conditions

A novel ordered mesoporous carbon nitride (OMCN) was synthesized as a functionalized support with 2,4,6-trichloro-1,3,5-triazine and benzidine as starting materials in the presence of SBA-15 as a template. Copper nanoparticles were then loaded on the C–N material to achieve a novel nanocomposite catalyst (Cu NPs-OMCN). The nanocomposite was utilized as a highly efficient catalyst for homo- and cross-coupling of terminal alkynes under base-free conditions in ethanol, and various symmetrical and unsymmetrical 1,3-diynes were obtained with good to excellent yields. Moreover, based on this reaction, a one-pot approach to synthesize 2,5-disubstituted thiophenes and furans from terminal alkynes were developed. Furthermore, the heterogeneous catalyst could be recovered and reused conveniently for several times with satisfactory yields.

Gold-Catalyzed Oxidative Coupling of Alkynes toward the Synthesis of Cyclic Conjugated Diynes

Gold-catalyzed oxidative coupling of alkynes was developed as an efficient approach for the synthesis of challenging cyclic conjugated diynes (CCD). Compared with the classic copper-promoted oxidative coupling reaction of alkynes, this gold-catalyzed process exhibited a faster reaction rate due to rapid reductive elimination from the Au(III) intermediate. This unique reactivity thus allowed a challenging diyne macrocyclization to take place with high efficiency. Condition screening revealed an [(n-Bu)4N]+[Cl-Au-Cl]? salt as the optimal pre-catalyst. Macrocycles with ring size between 13 and 28 atoms were prepared in moderate to good yields, which highlighted the broad substrate scope of this new strategy. Furthermore, the synthetic utilities of the CCDs for copper-free click chemistry have been demonstrated, showcasing the potential application of this strategy in biological systems. Macrocycles are important structural moieties in medicinal and biological research, and efficient methods for macrocyclization are always in high demand. With the unique conformation having six carbon atoms in a linear geometry, the cyclic conjugated diynes (CCD) present greater synthetic challenges and have been much less explored. Therefore, application of these unique macrocycles in biological studies is largely unexplored. Here, we describe the discovery of gold-catalyzed Glaser-Hay type oxidative coupling of terminal alkynes to achieve CCD under diluted conditions with broad substrate scope and great functional group compatibility. Taking advantage of the 14-member cyclic diyne, a copper-free click chemistry was achieved, which provided an effective alternative strategy for the traditional cyclooctyne-based azide-alkyne cycloaddition, suggesting a promising future for this method in tackling challenging problems in related biological and medicinal research. Gold-catalyzed oxidative coupling of alkynes was developed as an efficient approach for the synthesis of challenging cyclic conjugated diyne. Compared with copper-promoted oxidative coupling, this protocol allowed macrocyclization under dilute conditions with good overall reactivity and high functional group tolerance. The success in achieving copper-free click chemistry on cyclic conjugated diyne highlights its potential application in biological and medicinal research.

Copper Catalysis for Selective Heterocoupling of Terminal Alkynes

A Cu-catalyzed selective aerobic heterocoupling of terminal alkynes is disclosed, which enables the synthesis of a broad range of unsymmetrical 1,3-diynes in good to excellent yields. The results disprove the long-held belief that homocouplings are exclusively favored in the Glaser-Hay reaction.

Gold-catalyzed oxidative cross-coupling of terminal alkynes: Selective synthesis of unsymmetrical 1,3-diynes

Gold-catalyzed oxidative cross-coupling of alkynes to unsymmetrical diynes has been achieved for the first time. A N,N-ligand (1,10-Phen) and PhI(OAc)2 were identified as crucial factors to promote this transformation, giving the desired cross-

Rational design of a palladium-catalyzed Csp-Csp cross-coupling reaction inspired by kinetic studies

Less is More: A highly selective Pd-catalyzed Csp-Csp cross-coupling reaction between terminal alkynes and 1-bromoacetylenes has been developed. Catalyst loading is low (only 0.0001-0.01 mol % of Pd is required) and provides products with high selectivities and good to excellent yields under mild conditions. TBAB=tetrabutylammonium bromide, TON=turnover number. Copyright

Zinc-mediated enantioselective addition of terminal 1,3-diynes to N-arylimines of trifluoropyruvates

A facile and effective enantioselective addition of terminal 1,3-diynes to acyclic α-CF3 ketimine esters has been developed by using zinc/Binol complexes. The reaction works well with a variety of aromatic-, aliphatic- and silyl-substituted diynes, providing the desired products in up to 97% yield and 97% enantiomeric excess.

Nickel-catalyzed oxidative coupling reactions of two different terminal alkynes using O2 as the oxidant at room temperature: Facile syntheses of unsymmetric 1,3-diynes

(Formula Presented) Two different terminal alkynes now can be coupled together in the presence of NiCl2-6H2O/Cul by using an excess of one of the terminal alkyne substrates. The new method employed 20 mol % TMEDA as the ligand and environmentally benign O2 or air as the oxidant. It is the first example using Ni-salt as catalyst by employing air or O2 as oxidant, which led to efficient heterocoupling of two different alkynes.