64583-16-0

Upstream product

• 123-11-5 4-methoxy-benzaldehyde 
• 73584-06-2 diethyl α-chloro-4-fluorobenzylphosphonate 
• 766-98-3 1-ethynyl-4-fluorobenzene 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 60512-57-4 1-(2,2-dibromovinyl)-4-methoxybenzene 
• 437-29-6 tris(4-fluorophenyl)bismuthane 
• 5720-07-0 4-methoxyphenylboronic acid 
• 81233-93-4 2-methyl-4-(4-fluorophenyl)-3-butyn-2-ol 
• 460-00-4 1-Bromo-4-fluorobenzene 
• 33675-41-1 1-bromo-2-(4-methoxyphenyl)acetylene 
• 1765-93-1 4-fluoroboronic acid 
• 456-22-4 4-Fluorobenzoic acid 
• 768-60-5 4-methoxyphenylacetylen 
• 352-33-0 1-Chloro-4-fluorobenzene 

Downstream Products

• 1337541-94-2 (Z)-2-(4-fluorophenyl)-2-iodo-1-(4-methoxyphenyl)vinyl acetate 
• 1370552-47-8 3-(4-fluorophenyl)-4-iodo-2-(4-methoxyphenyl)-5-phenylfuran 
• 1370552-89-8 (E)-2-(4-fluorophenyl)-1-(4-methoxyphenyl)-4-phenylbut-1-en-3-yn-1-yl acetate 
• 1370552-70-7 (Z)-2-(4-fluorophenyl)-1-(4-methoxyphenyl)-4-phenylbut-1-en-3-yn-1-yl acetate 

Relevant academic research and scientific papers

Palladium-catalyzed decarbonylative sonogashira coupling of terminal alkynes with carboxylic acids

A direct decarbonylative Sonogashira coupling of terminal alkynes with carboxylic acids was achieved through palladium catalysis. This reaction did not use overstoichiometric oxidants, thus overcoming the homocoupling issue of terminal alkynes. Under the reaction conditions, a wide range of carboxylic acids including those bioactive ones could couple readily with various terminal alkynes, thus providing a relative general method for preparing internal alkynes.

Systematic studies on the effect of fluorine atoms in fluorinated tolanes on their photophysical properties

In this study, we synthesized a series of fluorinated and non-fluorinated tolanes, in which one or more fluorine atoms were systematically introduced into one aromatic ring of a tolane scaffold, and systematically evaluated their photophysical properties. All the tolanes with or without fluorine substituents were found to have poor photoluminescence (PL) in tetrahydrofuran (THF) solutions. On the other hand, in the crystalline state, non-fluorinated and fluorinated tolanes with one or four fluorine atoms were less emissive, whereas fluorinated tolanes with three or five fluorine atoms exhibited high PL efficiencies (φPL) up to 0.51. X-ray crystallographic analyses of the emissive fluorinated tolanes revealed that the position of the fluorine substituent played a key role in achieving a high φPL. Fluorine substituents at the ortho (2/6) and para (4) positions led to tight and rigid packing due to plural π–π stacking and/or hydrogen bonding interactions, resulting in enhanced φPL caused by the suppression of non-radiative deactivation. Additionally, fluorinated tolanes with three fluorine atoms exhibited notable aggregation-induced PL emission enhancement in THF/water mixed solvents. This demonstrates that the PL characteristics of small PL materials can be tuned depending on the usage requirements.

Synthesis of Unprotected and Highly Substituted Indoles by the Ruthenium(II)-Catalyzed Reaction of Phenyl Isocyanates with Diaryl/Diheteroaryl Alkynes/Ethyl-3-phenyl Propiolates

A one-pot transformation has been developed for the synthesis of unprotected and highly substituted indoles by an in situ installed carbamide-directed Ru(II)-catalyzed intermolecular oxidative annulation of phenyl isocyanates with diaryl/diheteroaryl alkynes/ethyl phenyl propiolates in the presence of Cu(OAc)2·H2O as an oxidant and AgSbF6 as an additive at 120 °C within 3 h.

Atom-Economical Thiocyanation-Amination of Alkynes with N-Thiocyanato-Dibenzenesulfonimide

A highly regioselective protocol for intermolecular thiocyanation-amination of alkynes by N-thiocyano-dibenzenesulfonimide (NTSI) as the SCN and nitrogen sources has been developed. A C-S bond and C-N bond are simultaneously constructed in only one step. The reaction under simple mild conditions features a broad substrate scope, atom economy, high yields (up to 94%), and excellent functional group tolerance.

LiHMDS-Promoted Palladium-Catalyzed Sonogashira Cross-Coupling of Aryl Fluorides with Terminal Alkynes

A highly efficient Pd-catalyzed Sonogashira coupling of various aryl fluorides with terminal alkynes in the presence of LiHMDS was developed. Both unreactive electron-rich fluoroarenes and electron-poor fluoroarenes proceeded smoothly and afforded the cor

Sonogashira Cross-Coupling of Aryltrimethylammonium Salts

A protocol for C(sp)-C(sp2) bond formation via the Sonogashira coupling reaction involving C-N bond cleavage with aryltrimethylammonium triflate as an electrophilic coupling partner is described in this work. The reactions proceeded well under mild conditions with a stoichiometric ratio of alkyl, aryl, or heteroaryl acetylenes and provided yields of up to 93%. Numerous useful functional groups were tolerated under the reaction conditions. Direct amine alkynylation can be achieved through a one-pot process without the isolation of ammonium salt. The protocol can be performed on a gram scale. Density functional theory calculations were performed to investigate the reaction mechanism that involved oxidative addition, alkyne coordination, deprotonation, and reductive elimination, which yielded the cross-coupling product.

A novel zinc-catalyzed Suzuki-type cross-coupling reaction of aryl boronic acids with alkynyl bromides

A novel Suzuki-type cross-coupling reaction of organoboron reagents with alkynyl bromides has been developed in the presence of catalytic Et2Zn/DMEDA system. The reaction afforded a variety of internal alkynes in moderate to excellent yields under mild reaction conditions without the formation of any homo-coupling products. The resulting internal alkynes have valuable applications in pharmaceutical and industrial areas. The use of relatively non-toxic zinc, chelating amine ligand and low reaction temperature make this protocol an alternative for the synthesis of internal alkynes. The scope and limitations of this protocol are also investigated.

Pd-catalyzed Sonogashira coupling in aqueous media. Observation of micelles that contain substrates and catalyst

Sonogashira-coupling of 4-iodoanisole with 4-methylphenylacetylene was conducted in the presence of Pd(II) catalyst, NEt3, CuI and sodium dodecylsulfonate (SDS) in aqueous media. The reaction catalyzed by PdCl2(Me2NCH2CH2NMe2) (2b) at 80 °C affords 4-methoxyphenyl-4′-methylphenylalkyne in 51% yield after 2.0 h, whereas those catalyzed by the complexes with other ethylenediamine derivatives, PdCl2(R2NCH2CH2NR2) (R[dbnd]H, C2H5, C3H7, C4H9, and C6H13), formed the product in lower yields (18–26%). Aqueous solution of complex 2b (5.3 mM) and SDS (168 mM) forms a yellow colloidal solution, which is stable for one night at room temperature. The complexes of ethylenediamines with higher alkyl substituents on the nitrogen atoms do not form apparently homogeneous solutions. TEM (transmission electron micrograph) observation of the former solution ([2b] = 5.3 mM), layered on a copper grid surface, revealed formation of Pd-containing micelles with diameters of ca. 4.0–6.0 nm A mixture of 2b (5.4 mM), 4-iodoanisole (125 mM) and 4-methylphenyl acetylene (250 mM) in water contains micelles with diameters smaller than 40 nm, as is clearly observed by TEM. Mixtures of the other complexes and the substrates contain micelles with larger sizes, and their TEM images are obscure. Thus, complex 2b forms small and clear micelles containing the catalyst and the substrate in the reaction mixture, and the micelle formation enhances the reaction in aqueous media.

Synthesis of Internal Alkynes through an Effective Tandem Elimination-Hydrodebromination-Cross-Coupling of gem-Dibromoalkenes with Halobenzenes

Carbon-carbon couplings are among the most important strategies for constructing functional molecules in organic synthetic chemistry, and cheap, diverse, and readily available coupling partners are crucial to these diverse reactions. In this contribution, we report the first palladium-catalyzed C-C cross-coupling reaction of two kinds of organic halide, a gem -dibromoalkene and a halobenzene, as the starting materials. Terminal alkynes were generated in situ through a tandem elimination-hydrodebromination process, and the internal alkyne final products were synthesized in one pot. The reaction proceeded under simple, facile, and classic copper-free Sonogashira coupling reaction conditions in good to excellent yields.

Cross-coupling reactivity of 1,1-dichloroalkenes under palladium catalysis: Domino synthesis of diarylalkynes

An efficient synthesis of diarylalkynes was achieved from the domino cross-coupling reaction of 1,1-dichloroalkenes with triarylbismuth reagents under palladium-catalyzed conditions. Under the established palladium protocol, 1,1-dichloroalkenes demonstrated hitherto unknown remarkable cross-coupling reactivity with organometallic triarylbismuth reagents to furnish functionalized diarylalkynes.