35070-01-0

Upstream product

• 3034-54-6 2-iodo-1,3-thiazole 
• 13146-23-1 copper(I) phenylacetylenide 
• 3034-53-5 2-bromo-1,3-thiazole 
• 536-74-3 phenylacetylene 
• 288-47-1 1,3-thiazole 
• 28995-88-2 1-methyl-4-((phenylethynyl)sulfonyl)benzene 
• 121-44-8 triethylamine 
• 3034-52-4 2-chlorothiazole 

Downstream Products

• 1031898-35-7 C₁₇H₁₆N₂O₂S 
• 35133-69-8 2-(6a-phenyl-1a,1b,6,6a-tetrahydro-1H-1,6-cyclo-cyclopropa[3,4]cyclobuta[1,2-a]inden-6b-yl)-thiazole 

Relevant academic research and scientific papers

Ligand-free Pd/Ag-mediated dehydrogenative alkynylation of imidazole derivatives

A variety of 2-alkynyl(benzo)imidazoles have been synthesized by dehydrogenative alkynylation of (benzo)imidazoles with terminal alkyne in NMP under air in the presence of Ag2CO3as the oxidant and Pd(OAc)2as the catalyst precursor. The data obtained in this study support a reaction mechanism involving a non-concerted metalation deprotonation (n-CMD) pathway.

Three Different Reactions, One Catalyst: A Cu(I) PNP Pincer Complex as Catalyst for C-C and C-N Cross-Couplings

An air-stable, thermally robust, and well-defined Cu(I) PNP pincer complex based on the 2,6-diaminopyridine scaffold is described. This complex is an active catalyst for the cross-couplings of a range of aryl and heteroaryl (including benzoxazole, thiazole, pyridine, and thiophene) halides with different organomagnesium reagents, alkynes, and aryl-amines giving excellent to good isolated yields.

A straightforward alkynylation of Li and Mg metalated heterocycles with sulfonylacetylenes

Coupling of alkynyl moieties to heterocyclic rings, without using transition metals, can be easily performed by the reaction of aryl or heteroaryl sulfonylacetylenes with heteroaryl-Li compounds or their corresponding less reactive magnesium derivatives.

Pd/tetraphosphine catalytic system for Cu-free Sonogashira reaction "on water"

An efficient copper-free Sonogashira coupling reaction was performed on water at 100 °C with N,N,N′,N′-tetra(diphenylphosphinomethyl) pyridine-2,6-diamine (1) as a ligand, [Pd(η3-C3H 5)Cl]2 as a catalyst precursor and K3PO 4 as a base. Both aryl and heteroaryl halides were successfully alkynylated in this system, and a high turnover number (TON) up to 860000 was obtained with a catalyst loading as low as 1 ppm.

Synthesis of internal alkynes through the Pd-catalyzed coupling of heteroaryl halides with terminal alkynes

Sonogashira-type cross-couplings of functionalized heterocyclic halides with terminal alkynes were performed efficiently at room temperature. The heteroaryl halides were easily prepared from the corresponding heterocyclic compounds. The catalytic system tolerated a very broad scope of substrates; oxazoles, thiazoles, and furans participate in this type of reaction for the first time. This reaction provides an efficient method for the direct functionalization of heterocycles. Sonogashira-type cross-coupling of functionalized heterocyclic halides with terminal alkynes are performed efficiently at room temperature. The catalytic system tolerates a very broad scope of substrates; oxazoles, thiazoles, and furans participate in this type of reaction for the first time. The reaction provides an efficient method for the direct functionalization of heterocycles. Copyright

Structure-Activity Relationships for Negative Allosteric mGluR5 Modulators

A series of compounds based on the mGluR5-selective ligand 2-methyl-6-(phenylethynyl)pyridine (MPEP) were designed and synthesized. The compounds were found to be either structural analogues of MPEP, substituted monomers, or dimeric analogues. All compounds retained mGluR5 selectivity with only weak or no activity at other mGluRs or iGluRs. The substituted analogue, 1,3-bis(pyridin-2-ylethynyl)benzene (19), is a potent negative modulator at mGluR5, whereas all other compounds lost potency relative to MPEP and showed that activity is highly dependent on the position of the nitrogen atom in the pyridine moieties. A homology modeling and ligand docking study was used to understand the binding mode and the observed selectivity of compound 19.

Highly efficient Pd/tetraphosphine catalytic system for copper-free sonogashira reactions of aryl bromides with terminal alkynes

In this study, an easily synthesized polydentate ligand N,N,N',N'-tetra(diphenylphosphinomethyl)-1,2-ethylenediamine (1) in combination with [Pd(C3H5)Cl]2 was found to be an active catalyst in copper-free Sonogashira reactions. Most substrates, including steric hindered phenyl bromides and heteroaryl bromides, could couple efficiently with terminal alkynes in the presence of low catalyst loading (0.1 mol%) and this catalytic system showed excellent functional group tolerance. The influence of water in this system was also preliminarily investigated via 31P NMR in situ; that is, appropriate water favors the reaction while excess hindered this reaction.

Palladium-catalyzed C-H bond direct alkynylation of 5-membered heteroarenes: A well-defined synthetic route to azole derivatives containing two different alkynyl groups

A widely applicable oxidative coupling of 5-membered heteroarenes and terminal alkynes that uses a combination of palladium and silver salts was developed. Under suitable conditions, imidazole and benzimidazole, which are sluggish under similar previously reported oxidative coupling conditions, as well as imidazo[1,5-a]pyridines, oxazole, benzoxazole, thiazole, and benzothiazole could be alkynylated. In addition, the bromine atom on the substrates was intact under the reaction conditions, and conventional Sonogashira coupling did not occur at all. With these reactivities in hand, a well-defined synthetic route to imidazo[1,5-a]pyridines and thiazole containing two different alkynyl groups was achieved in a simple manner. In addition, linear correlations were observed between the fluorescence wavelength and the Hammett substituent constants of aryl groups, not only on the C1- but also on the C3-alkynyl group of the obtained 1,3-bis(arylethynyl)imidazo [1,5-a]pyridines.

A straightforward copper-free palladium methodology for the selective alkynylation of a wide variety of S-, O-, and N-based mono- and diheterocyclic bromides and chlorides

High-yield alkynylations are successfully achieved by a simple and widely accessible catalytic system for an unprecedented variety of heterocyclic bromides and chlorides in position -2, -3 or -5: pyridine, quinoline, thiophene, furan, thiazole, benzothiazole, pyrimidine, pyridazine, pyrazine, dioxepin halides are efficiently functionalized in short time reactions. This copper-free methodology employs 1 mol % palladium only, with inexpensive PPh3 and amine base. The ionic liquid solvent allows a straigtforward separation of products and recycling opportunity. Unsuitable substrates and secondary reactions are also reported in order to point out further progress in cross-coupling using ionic liquids.

Reusable Cu2O/PPh3/TBAB system for the cross-couplings of aryl halides and heteroaryl halides with terminal alkynes

(Chemical Equation Presented) An efficient and reusable Cu 2O/PPh3/TBAB (n-Bu4NBr) system for the cross-coupling reactions of aryl and heteroaryl halides with terminal alkynes has been developed. Four types of Cu2O, including bulky Cu 2O, cubic Cu2O nanoparticles, octahedral Cu2O nanoparticles, and spherical Cu2O nanoparticles, were examined, and the octahedral Cu2O nanoparticles were found to be the most effective catalyst for the reaction. In the presence of the octahedral Cu2O nanoparticles, PPh3, and TBAB, a variety of aryl and heteroaryl halides were reacted with alkynes including alkynols smoothly in moderate to good yields. Noteworthy is that the Cu2O/ PPh3/TBAB system can be recovered and reused several times without loss of any activities.