10371-50-3

Upstream product

• 1455-18-1 3-methylbenzothiophene 
• 71-43-2 benzene 
• 673-32-5 1-Phenylprop-1-yne 
• 19614-16-5 2-bromo-1-(methylsulfanyl)benzene 
• 108-86-1 bromobenzene 
• 934-87-2 S-phenyl thioacetate 
• 33775-94-9 2-(methylthio)iodobenzene 
• 1562410-37-0 (E)-2-(2-(methylsulfinyl)phenyl)-1-phenyl-1-propene 
• 5698-59-9 benzo[c]thiophene-1,3-dione 
• 591-50-4 iodobenzene 
• 98-80-6 phenylboronic acid 
• 3133-78-6 3-methylbenzo[b]thiophene-2-carboxylic acid 

Relevant academic research and scientific papers

Potassium Hydroxide/Dimethyl Sulfoxide Superbase-Promoted Transition Metal-Free Synthesis of 2-Substituted Benzothiophenes under Visible Light

A potassium hydroxide/dimethyl sulfoxide (KOH/DMSO) superbase-promoted method for the synthesis of 2-substituted benzothiophenes has been developed via photoinduced intermolecular annulation of 2-halothioanisoles with terminal alkynes at ambient temperature. The present protocol uses commercially available 2-halothioanisoles as substrates and visible light as energy force, which offers a wide range of benzothiophenes regioselectively in moderate to good yields. Such a facile and effective transformation will provide an environment-friendly approach to the synthesis of benzothiophene derivatives.

Novel phenyl migration of 1-phenylbenzo[b]thiophenium triflates in the thermolysis

Thermolysis of 1-phenylbenzo[b]thiophenium triflates at 180°C causes phenyl migration to give 2-phenylbenzo[b]thiophenes in high yields. Interestingly, the thermolysis of 1-phenylbenzo[b]thiophenium triflates having a substituent at the 2 position affords

Phenyl migration to thiophene ring in photolysis of 1-phenylbenzo[b]thiophenium salts

Photolysis of 1-phenylbenzo[b]thiophenium salts was conducted by use of a Pyrex-filtered high pressure Hg lamp. The major products in most cases were the phenyl-migrated ones, i.e., 2-phenylbenzo[b]thiophenes and 3-phenylbenzo[b]thiophenes, together with the dephenylated benzo[b]thiophenes. This photochemical behavior is quite different from the thermal ones that provide the ring-opened olefins. The selective phenyl migration to the thiophene ring and the absence of the ionic products are characteristic of benzothiophenium systems.

A Convoluted Polyvinylpyridine-Palladium Catalyst for Suzuki-Miyaura Coupling and C?H Arylation

The development of highly active and reusable supported catalysts for Suzuki-Miyaura coupling and catalytic C?H arylation is important for fundamental and applied chemistry, with these reactions being used to produce medical compounds and functional materials. Herein, we found that a mesoporous composite made of a linear poly(4-vinylpyridine) and tetrachloropalladate acted as a dual-mode catalyst for a variety of cross-coupling reactions, with both Pd nanoparticles and a Pd complex catalyst being observed under different conditions. The polyvinylpyridine-palladium composite 1 was readily prepared via the molecular convolution of poly(4-vinylpyridine) and sodium tetrachloropalladate to provide a hardly soluble polymer-metal composite. The Suzuki-Miyaura coupling and the C?H arylation of aryl chlorides and bromides with arylboronic acids, thiophenes, furans, benzene, and anisole proceeded in the presence of 0.004 mol% (40 mol ppm) to 1 mol% Pd of 1 to afford the corresponding coupling products in high yields. Furthermore, the catalyst was reused without an appreciable loss of activity. Pharmaceutical compounds and functional materials were synthesized via the coupling reactions. N2 gas adsorption/desorption analysis indicated that the catalyst had a mesoporous nature, which played a crucial role in the catalysis. In the Suzuki-Miyaura couplings, in situ generated palladium nanoparticles in the polymer matrix were catalytically active, while a polymeric Pd(II) complex was crucial in the C?H arylations. These catalytic species were investigated via XAFS, XPS, far-infrared absorption, and Raman spectroscopies, as well as DFT calculations. (Figure presented.).

Nickel-catalyzed and Li-mediated regiospecific C-H arylation of benzothiophenes

A nickel-based catalytic system for the regiospecific C2-H arylation of benzothiophene has been established. NiCl2(bpy) is used as a catalyst in combination with LiHMDS as a base in dioxane. The catalytic system is applicable to a variety of functionalized benzothiophenes, as well as other heteroarenes including thiophene, benzodithiophene, benzofuran and selenophene in combination with iodo aryl electrophiles. The role of LiHMDS as a uniquely potent base and a postulated mechanism are discussed. The applicability of this system is finally demonstrated for the synthesis of an intermediate of an active pharmaceutical ingredient.

Integration of a Four-Step Reaction into One-Pot under the Coexistence of Silica-Gel-Supported Acid and Base Reagents: Synthesis of Benzo- and Naphthothiophenes Using NaHSO 4 /SiO 2 and Na 2 CO 3 /SiO 2

A four-step synthesis of benzo- and naphthothiophenes that have biological importance and application in material science was integrated into a one-pot reaction by using silica gel-supported acid and base reagents, NaHSO 4 /SiO 2 and Na 2 CO 3 /SiO 2. The supported reagents provided acid and base environments on the surface of the supports without neutralization and worked separately in the same medium. The four-step reaction comprises (i) deacetylation of 3-halo-2,4-pentanediones to α-halo ketones, (ii) deacetylation of S -aryl thioacetates to arenethiols, (iii) coupling of α-halo ketones and arenethiols to give α-sulfanyl ketones, and (iv) cyclization of sulfanyl ketones to benzo- and naphthothiophenes. The steps (i) and (iii) proceeded by Na 2 CO 3 /SiO 2, and (ii) and (iv) by NaHSO 4 /SiO 2. The four-step reaction proceeded efficiently by introduction of starting materials and reagents in a single reaction vessel. The starting materials were very easy to handle and unpleasant smell of aryl thiols that were used in conventional methods could be avoided. Novel thirty-nine benzo- and naphthothiophenes were synthesized by this method in excellent to fair yields.

Decarboxylative Suzuki-Miyaura coupling of (hetero)aromatic carboxylic acids using iodine as the terminal oxidant

A novel methodology for the decarboxylative Suzuki-Miyaura-type coupling has been established. This process uses iodine or a bromine source as both the decarboxylation mediator and the terminal oxidant, thus avoiding the need for stoichiometric amounts of transition metal salts previously required. Our new protocol allows for the construction of valuable biaryl architectures through the coupling of (hetero)aromatic carboxylic acids with arylboronic acids. The scope of this decarboxylative Suzuki reaction has been greatly diversified, allowing for previously inaccessible non-ortho-substituted aromatic acids to undergo this transformation. The procedure also benefits from low catalyst loadings and the absence of stoichiometric transition metal additives.

Palladium-Catalyzed Synthesis of 2,3-Disubstituted Benzothiophenes via the Annulation of Aryl Sulfides with Alkynes

A new method has been developed for the synthesis of 2,3-disubstituted benzothiophenes involving the palladium-catalyzed annulation of aryl sulfides with alkynes. This convergent approach exhibited good functional group tolerance, providing rapid access to a diverse array of derivatives from simple, readily available starting materials. This protocol can also be used to synthesize 2-silyl-substituted benzothiophenes, which can be used as versatile platforms for the synthesis of 2,3-unsymmetrically substituted benzothiophenes.

Rhodium(III)-catalyzed ortho -alkenylation through C-H bond cleavage directed by sulfoxide groups

The rhodium-catalyzed ortho-alkenylation of phenyl sulfoxides using alkenes or alkynes as substituent sources proceeds efficiently through sulfoxide group directed C-H bond cleavage to produce the corresponding o-alkenylphenyl sulfoxides. The products rea

Palladated oligophenylene thioethers: Synthesis and reactivity toward isocyanides, carbon monoxide, and alkynes

Phenylene thioethers XC6H4(SC6H 4R-4)-a (a = 2, 4; X = Br, I; R = H, OMe, NO2) react with Pd(dba)2 and 2 equiv of PPh3 or 1 equiv of 2,2′-bipyridine (bpy) to afford trans-[PdBr{C6H 4(SC6H4R-4)-a}(PPh3)2 (for example, a = 2, R = H (1)) or cis-[PdI{C6H4(SC 6H4R-4}-a)(bpy) (for example, a = 2, R = H (5)), respectively. Complex 1 (as well as some of its homologues) reacts (1) with 1 equiv of [PdCl2(NCPh)2 to give a mixture of isomers of [{PdBr(PPh3)}2(μ-C,S-C6H4SPh-2) 2, (2) with 1 equiv of XyNC (Xy = C6H3Me 2-2,6) to render SP-4-4-[PdBr{C,S-C(=NXy)C6H 4-2-SPh}(PPh3), (3) with XyNC and TlTfO (TfO = O 3SCF3; 1:2:1 molar ratios) to give SP-4-3-[Pd{C,S-C(=NXy) C6H4-2-SPh}(CNXy)(PPh3)TfO, (4) with 4 equiv of XyNC to give SP-4-4-[Pd{C,N-C(=NXy)C(=NXy)C(=NXy)C6H 4(SPh)-2}Br(CNXy), or (5) with TlTfO (1:1 molar ratio) to afford a mixture of compounds from which a few single crystals of (Ph3PC 6H4SPh-2)TfO could be obtained. Complexes with bpy ligands react with 2 equiv of PPh3 to give trans-[PdI{C6H 4(SC6H4R-4)-4}(PPh3)2 or with 3 equiv of XyNC affording monoinserted complexes resulting from the replacement of the PdI(bpy) group by trans-{C(=NXy)}Pd(CNXy)2. Dinuclear complexes are prepared by reacting diiodophenylene thioethers with Pd(dba)2 and bpy. Complex 5 reacts with TlTfO and CO or various alkynes RC≡CR′ to afford, respectively, [Pd{C,S-C(O)C 6H4SPh-2)}bpyTfO or [Pd{C,S-C(R′)=C(R)C 6H4SPh-2}bpy, the latter of which decompose thermally to give the benzothiophenes resulting from the C-S coupling. Crystal structures of some model complexes have been determined.