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A simple and efficient protocol for the Heck reaction of cyclic alkenones with electron-rich aryl bromides has been developed. A ligand combination of X-Phos and tri-tert-butylphosphonium hydrogen tetrafluoroborate in the presence of Pd(PPh3)2Cl2 and Na2CO3 in DMSO was found to be efficient and selective for electron-rich aryl bromides with high substrate scope for cyclic alkenones.

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Reference:
Benzothiophene – Wikipedia,
Benzothiophene | C8H6S – PubChem

 

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A novel series of benzo[b]thiophene diamine thrombin inhibitors with a conformationally restricted C3-side chain 3 was investigated. The constrained C3-side chain by a cyclohexyl ring contributed to not only an additive but also a synergistic effect on the thrombin inhibitory activity. The SAR studies resulted in the discovery of a potent thrombin inhibitor 27 that was over 750-fold more potent than the initial lead compound 1.

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A protocol for the Pd-catalyzed hydroxycarbonylation of aryl iodides, bromides, and chlorides has been developed using only 1-5 mol % of CO, corresponding to a pCO as low as 0.1 bar. Potassium formate is the only stoichiometric reagent, acting as a mildly basic nucleophile and a reservoir of CO. The substoichiometric CO could be delivered to the reaction from an acyl-Pd(II) precatalyst, which provides both the CO and an active catalyst, and thereby obviates the need for handling a toxic gas.

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Benzothiophene – Wikipedia,
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Novel 2-sulfamoylbenzo[b]thiophenes and derivatives thereof are shown to be useful for the treatment of elevated intraocular pressure in compositions including ophthalmic drops and inserts.

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A highly efficient method of visible light mediated Ni(II)-catalyzed photoredox N-arylation of Cbz-amines/Boc-amines with aryl electrophiles at room temperature is reported. The methodology provides a common access to a wide variety of N-aromatic and N-heteroaromatic carbamate products that find use in the synthesis of several biologically active molecules and provides a distinct advantage over traditional palladium-catalyzed Buchwald reaction.

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For the first time, an approach to 3,4-disubstituted thietes was developed through two complementary paths. While the first one relies on alpha-metalation, the second is based on direct C-H functionalization. A new library of sophisticated sulfur-containing four-membered rings is described, paving the way to new bioactive analogues and small heterocycle incorporation.

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A copper-catalyzed borylation/benzylic cyanation of vinylarenes whose regioselectivity is seemly common but scarcely achieved is reported. This unprecedented regioselectivity is realized through a structure-distinctive cyanating reagent, dimethylmalononitrile. This reaction can be applied to both ?-extended and simple vinylarenes with various diboron reagents, and it exhibits good functional group compatibility. With the ample transformations of cyano and boronate groups, this reaction provides expedient access to complex organic structures.

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A facile oxidation for the clean conversion of benzo[b]thiophenes to their corresponding sulfones is described employing an aqueous solution of H 2O2 and P2O5; the solution can be prepared and stored on a multi-gram scale with a shelf-life of up to two weeks.

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The in situ generation of a “cyano” unit from readily available organic precursors is of high interest in synthetic chemistry. Herein, we report the first example of Ni-mediated dehydration of formamide to form “CN” and its subsequent catalytic applications in the hydrocyanation of alkynes and cyanation of aryl halides. Formamide can serve as a convenient source for the nitrile unit, in that it releases water as the only byproduct.

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Divergent synthesis that enables a catalytic reaction to selectively produce different products from common substrates will allow the charting of wider chemical space and the unveiling of distinct mechanistic paradigms. A common strategy for it employs different ligands to modulate organometallic catalysts. Dramatic developments in photocatalysis have enabled previously inaccessible transformations. In particular, photoredox catalysis modulates the oxidation state of transition-metal complexes, offering enormous opportunities for methodology development. Herein, we developed a photo-mediated divergent ethylene difunctionalization via modulating oxidation states of the nickel catalyst by using different photoredox catalysts. This work will inspire new perspectives for value-added chemical synthesis using ethylene as a feedstock and shed light on photoredox-catalyst-based divergent synthesis, which fundamentally differs from ligand-controlled transition-metal catalysis.Divergent synthesis represents a powerful strategy for directly accessing different molecular scaffolds originating from the same starting materials. Access to different end products via transition-metal catalysis is conventionally achieved by ligand control. We herein demonstrate the use of ethylene feedstock and commercially available aryl halides to accomplish the divergent synthesis of 1,2-diarylethanes, 1,4-diarylbutanes, or 2,3-diarylbutanes in a highly selective fashion through the synergistic combination of nickel and photoredox catalysis. Mechanistic studies suggest that the observed selectivity was due to different active states of Ni(I) and Ni(0) modulated by Ru- and Ir-based photoredox catalysts, respectively. The ability to access different organometallic oxidation states via photoredox catalysis promises to inspire new perspectives for synergistic transition-metal-catalyzed divergent synthesis.Functionalization of ethylene without polymerization is challenging under photo-irradiation conditions. We have demonstrated that the photo-transformation of ethylene can be controllable by merging photoredox and transition-metal catalysis. In our study, the use of different photoredox catalysts was able to modulate the oxidation state of the nickel catalyst. Through different oxidation states, the nickel-catalyzed couplings proceeded via distinct pathways to generate divergent ethylene difunctionalization products selectively from the same feedstock.

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Reference:
Benzothiophene – Wikipedia,
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