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The pair NaBH4-TMEDA as a hydride source and catalytic PdCl 2(dppf) in THF prove to be an efficient system for the hydrodehalogenation of bromo(chloro)-heteropentalenes with one or two heteroatoms, while Pd(OAc)2/PPh3 is able to reduce reactive haloheteropentalenes, and PdCl2(tbpf) allows the removal of the 2-chlorine from a thiophene ring. The reaction conditions tolerate various functional groups, allowing highly chemoselective reactions in the presence of halide, ester, alkyne, alkene, and nitrile substituents and also showing good efficiency in the regioselective hydrodehalogenation of a variety of polyhalogenated substrates.

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

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Over the last 20 years, there has been significant progress in the direct CH (het)arylation chemistry of a wide variety of (het)arenes. Herein, the application of direct CH arylation on the 1,2-azoles: pyrazoles, isothiazoles, and isoxazoles and their annulated analogues is reviewed starting from the first arylation methods on 1,2-azoles until 2018.

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Benzothiophene – Wikipedia,
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Eight new compounds, including three new ring systems obtained via the Friedlunder condensation of ortto-aminothiophenecarbaldehydes 11, 21 and 24 with creatinine (8), are reported. The condensation afforded 1, which is the thieno analogue of the cooked-food mutagen IFP (2-amino-1,6-dimethylfuro[2,3-e] imidazo[4,5-b]pyridine), and the benzothieno[2,3-e]- and benzothieno[3,2-e] imidazo[4,5-b]pyridines 2 and 3. Attempts to condense 11 with isocreatinine (12) were unsuccesful. Desulfurization of 3 gave the known cooked-food carcinogen PhIP, The 2-nitro (4) and 2-hydroxy (5) derivatives of 3 are reported. The related 2-amino-1-methyl-imidazo[4,5-b]benzothiophene (25) was synthesized by a different route. Fully assigned 1H and 13C nmr data of all new compounds are reported.

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

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Ready for action: An excellent quantum yield was observed for a photocoloration reaction of a photochromic molecule based on a triangular terarylene structure. The molecule is brought into a conformation favorable for photocyclization by multiple intramolecular interactions, including CHi-N hydrogen bonding and Si-N and CHi-pi interactions (see picture).

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

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Methods for the conversion of aliphatic acids to alkyl halides have progressed significantly over the past century, however, the analogous decarboxylative bromination of aromatic acids has remained a longstanding challenge. The development of efficient methods for the synthesis of aryl bromides is of great importance as they are versatile reagents in synthesis and are present in many functional molecules. Herein we report a transition metal-free decarboxylative bromination of aromatic acids. The reaction is applicable to many electron-rich aromatic and heteroaromatic acids which have previously proved poor substrates for Hunsdiecker-type reactions. In addition, our preliminary mechanistic study suggests that radical intermediates are not involved in this reaction, which is in contrast to classical Hunsdiecker-type reactivity. Overall, the process demonstrates a useful method for producing valuable reagents from inexpensive and abundant starting materials.

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

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The highly emissive B?N unit containing four-coordinate C,N-chelated organoboron compound, 2 was synthesized. This air and moisture stable compound can be used as a turn-off type fluorescent fluoride (F?) sensor in THF with good selectivity and reversibility. The DFT calculation and the fluorescence quenching titration results showed that the mechanism of the sensing process was based on a competing reaction: the formation of 2-F with the stronger B[sbnd]F bond in an open form took the place of 2 with B?N bond in a closed form when F? was introduced, leading to significant absorption changing and fluorescence quenching.

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Reference£º
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

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2,3-Disubstituted benzo[b]thiophenes, 1,3-disubstituted benzo[c]thiophenes, and 1,3-disubstituted benzo[c]selenophene have been systematically and selectively synthesized from benzo[b]thiophene or phthaloyl dichloride as a starting material, respectively. Characterization of the molecules was performed by physical and spectroscopic means and X-ray crystallographic analyses. The cyclic voltammograms of the chalcogenophene derivatives containing aryl fragments showed well-defined reversible both anodic and cathodic steps derived from the unusually stable 5pi chalcogenophene radical cations and 7pi chalcogenophene radical anions. The cyclic voltammograms of the novel chalcogenophene derivatives containing ferrocenyl fragments showed a well-defined reversible cathodic step derived from the unusually stable 7pi chalcogenophene radical anions and two distinct reversible anodic steps derived from ferrocenium cations separated from each other by a thiophene-heterocycle. The radical character of several novel 7pi chalcogenophene radical anions was measured by ESR spectroscopy.

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Benzothiophene – Wikipedia,
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The synthesis of silacycles is highly appealing due to their important applications in organic synthesis, medicinal chemistry, and materials chemistry. However, sila-tetralins and sila-benzosuberanes are surprisingly under-represented due to a lack of general methods to access these compounds. We successfully developed a Pd-catalyzed strain-release silicon-based cross-coupling as an unprecedented ring-expansion method, which constitutes a general route for preparing diverse sila-tetralins and sila-benzosuberanes.

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Two tri(benzo[b]thiopheno)subporphyrazine regioisomers with C3 and C1 molecular symmetry have been isolated from the cyclotrimerization of benzo[b]thiophene-2,3-dicarbonitrile as the first five-membered-heterocycle-fused subphthalocyanine analogues. Optical resolution of both regioisomers was achieved by using a chiral HPLC technique, affording the first chiral subphthalocyanine analogues.

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Benzothiophene – Wikipedia,
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Cope Rearrangements in the Benzothiophene Series

The inability to observe Cope rearrangement products at elevated temperatures for diethyl alpha-allyl-2-naphthalenemalonate (1) and diethyl alpha-allyl-9-phenanthrenemalonate (2) does not extend to the analogous systems resulting from replacement of the aromatic units by 2- and 3-benzothiophene nuclei.Thermal rearrangement of diethyl alpha-allyl-3-benzothiophenemalonate (5) at 215-255 deg C for 11 h produces the expected Cope rearrangement product diethyl 2-allyl-3-benzothiophenemalonate (10) (8percent) accompanied by trans- and cis-ethyl 2,3-dihydro-1-(ethoxycarbonyl)-1H-benzocyclopentathiophene-2-acetate (9a) (10percent) and (9b) (5percent), respectively.The structure elucidation of 10, 9a, and 9b was done by spectroscopy.The attempted structure verification of 10 by an independent route gave diethyl 2-(1-propenyl)-3-benzothiophenemalonate (12) which when heated at 230-240 deg C for 18 h gave 1-carbethoxy-2-hydroxy-3-methyldibenzothiophene (16) as a major product.Similar results were observed with 2-substituted analogues of 5, both diethyl 3-allyl-2-benzothiophenemalonate (24) and ethyl 1,2-dihydro-3-(ethoxycarbonyl)-3H-benzocyclopentathiophene-2-acetate (25) being formed.In this case the structure of 24 was verified by synthesis.An extension of this involved a study of thermal rearrangement of analogous compound ethyl alpha-allyl-alpha-cyano-3-benzothiopheneacetate (30).Thermal rearrangement of 30 at 235-245 deg C for 8 h gave the expected Cope rearrangement product ethyl alpha-cyano-2-allyl-3-benzothiopheneacetate (32) (6percent) along with an unexpected diastereomeric mixture of 1-cyano-1-(ethoxycarbonyl)-2-methyl-2,3-dihydro-1H-benzocyclopentathiophenes (33) (18percent).Speculative mechanistic considerations are offered regarding the mode of transformation of 12 to 16 and 32 to 33.

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem