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In the present work, we report the fabrication of a highly versatile ruthenium-based magnetically recoverable photoredox nanocatalyst with a large surface area. This visible light harvesting nanocatalyst was effectively used for cross-dehydrogenative coupling via C-H activation between tertiary amines and various carbon nucleophiles with high regioselectivity to afford the C-C coupled products in good to excellent yield using air as an oxidant under ambient conditions. The Ru-based catalyst was found to be a potential candidate from economical and environmental perspectives due to its magnetic recoverability and reusability.

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Tetrahydroisoquinoline – Wikipedia,
1,2,3,4-Tetrahydroisoquinoline | C9H11N – PubChem

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The photoredox-catalyzed coupling of N-aryltetrahydroisoquinoline and Michael acceptors was achieved using Ru(bpy)3Cl2 or [Ir(ppy)2(dtb-bpy)]PF6 in combination with irradiation at 455 nm generated by a blue LED, demonstrating the trapping of visible light generated alpha-amino radicals. While intermolecular reactions lead to products formed by a conjugate addition, in intramolecular variants further dehydrogenation occurs, leading directly to 5,6-dihydroindolo[2,1-a] tetrahydroisoquinolines, which are relevant as potential immunosuppressive agents.

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The title compounds are a class of structurally simple analogues of quaternary benzo[c]phenanthridine alkaloids (QBAs). In order to develop novel QBA-like antifungal drugs, in this study, 24 of the title compounds with various substituents on the N-phenylring were evaluated for bioactivity against seven phytopathogenic fungi using the mycelial growth rate method and their SAR discussed. Almost all the compounds showed definite activities in vitro against each of the test fungi at 50 mug/mL and a broad antifungal spectrum. In most cases, the mono-halogenated compounds 2-12 exhibited excellentactivities superior to the QBAs sanguinarine and chelerythrine. Compound 8 possessed the strongest activities on each of the fungi with EC50 values of 8.88-19.88 mug/mL and a significant concentration-dependent relationship. The SAR is as follows: the N-phenyl group is a high sensitive structural moiety for the activity and the characteristics and position of substituents intensively influence the activity. Generally, electron-withdrawing substituents remarkably enhance the activity while electron-donating substituents cause a decrease of the activity. In most cases, ortha- and para-halogenated isomers were more active than the corresponding m-halogenated isomers. Thus, the title compounds emerged as promising lead compounds for the development of novel biomimetic antifungal agrochemicals. Compounds 8 and 2 should have great potential as new broad spectrum antifungal agents for plant protection.

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The ruthenium carbamate complex derived from 3-trimethoxysilyl-1-propyl amine and carbon dioxide was found to be a novel catalyst for the oxidative cyanation of aromatic and cyclic tertiary amines to corresponding alpha-amino nitriles in high to excellent yields by using hydrogen peroxide and molecular oxygen as enviro-economic oxidants. The developed protocol suggested an efficient alternative for recycling carbon dioxide.

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RuCl3-catalyzed oxidative cyanation of tertiary amines with sodium cyanide under molecular oxygen (1 atm) at 60 C gives the corresponding alpha-aminonitriles, which are versatile synthetic intermediates of various compounds such as amino acids and unsymmetrical 1,2-diamines, in excellent yields. This reaction is clean and should be an environmentally benign and useful process. Copyright

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A general new method for the highly concise synthesis of C-1-alkylated tetrahydroisoquinolines (THIQ) is reported. The CuCl2-catalyzed procedure is based on a coupling of nonfunctionalized THIQs with organozinc reagents under aerobic conditions. It proceeds in high yields and is broadly applicable to a wide range of substrates. It relies on a regioselective sp3 C-H bond activation allowing for an sp3-sp3 bond union under mild reaction conditions in a rapid and effective manner. Mechanistically it involves an iminium ion intermediate that is formed via an organic radical involving a single-electron-transfer process. For the first time for this type of reaction a radical intermediate has been proven by EPR spectroscopy.

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A direct vinylogous cross-dehydrogenative coupling (CDC) reaction of N-aryl tetrahydroisoquinolines with 3,5-dialkyl-4-nitroisoxazoles catalysed by CuBr using air as the oxidant in water has been developed. This new strategy provides an efficient and environmentally benign way to access medicinally important isoxazole substituted tetrahydroisoquinoline derivatives under mild conditions.

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Pd-catalyzed intermolecular aerobic dehydrogenative aromatizations have been developed for the arylation of amines with nonaromatic ketones. Under optimized reaction conditions, primary and secondary amines are selectively arylated in good yields with cyclohexanones and 2-cyclohexen-1-ones in the presence of a Pd-catalyst under an atmosphere of molecular oxygen.

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Tetrahydroisoquinoline – Wikipedia,
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Binuclear copper complex [{Cu(Sal)2(NCMe)}2] (Sal=salicylate) was found to be an active catalyst for the aerobic oxidation of N-aryl tetrahydroisoquinolines to the corresponding iminium ions, which could be trapped by a wide range of nucleophiles to form coupled products. The reactions took place under 1 bar of O2 at room temperature with 1 mol % of the copper catalyst being sufficient in most cases, and are considerably accelerated by catalytic chloride anions. Mechanistic studies show that the CuII dimer oxidizes the amine to the iminium ion, and this two-electron process requires O2, whereby the resulting CuI is concomitantly reoxidised back to CuII. Various lines of evidence suggest that the oxidative coupling reaction is turnover-limited by the step of iminium formation, and it is this step that is promoted by the chloride anion. Since it is more efficient than and mechanistically distinct from the well-studied simple copper salts such as CuBr and CuCl2, the binuclear copper catalyst provides a new tool for oxidative coupling reactions.

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Selective cross-dehydrogenative coupling of N-phenyltetrahydroisoquinoline with carbon nucleophiles such as dimethyl malonate, ethyl acetoacetate, and nitromethane was demonstrated in complete aqueous media using poly(2-methoxyaniline-5-sulfonic acid)/gold nanoparticles under molecular oxygen.

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