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A decarboxylative alkylation of benzylic C(sp3)-H bonds of N-aryl tetrahydroisoquinolines under the irradiation of blue light is reported, featuring a broad substrate scope, low cost, heavy-metal-free, and mild conditions. A preliminary mechanistic study indicated that radical intermediates are involved during the course of the reaction.

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

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Our previous studies into visible-light-mediated aza-Henry reactions demonstrated that molecular oxygen played a vital role in catalyst turnover as well as the production of base to facilitate the nucleophilic addition of nitroalkanes. Herein, improved conditions for the generation of iminium ions from tetrahydroisoquinolines that allow for versatile nucleophilic trapping are reported. The new conditions provide access to a diverse range of functionality under mild, anaerobic reaction conditions as well as mechanistic insights into the photoredox cycle.

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

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Potassium ions cationized polyether cyanide [K+{PEG}CN-] was readily synthesized by mixing potassium cyanide and PEG400 at room temperature and used as a cost effective and comparatively safer alternative to the toxic sodium cyanide/acetic acid system for generating in situ HCN for the oxidative cyanation of tertiary amines with hydrogen peroxide using RuCl3 as catalyst. This method affords a facile approach to the synthesis of alpha-aminonitriles in high yields under solvent-free and acid-free reaction conditions.

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

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Ruthenium porphyrins (particularly [Ru(2,6-Cl2tpp)CO]; tpp = tetraphenylporphinato) and RuCl3 can act as oxidation and/or Lewis acid catalysts for direct C-3 alkylation of indoles, giving the desired products in high yields (up to 82% based on 60-95% substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron-withdrawing or electron-donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N-arylindoles to 3{[(N-aryl-N-alkyl)amino]methyl} indoles (yield: up to 82%, conversion: up to 95%) and the alkylation of N-alkyl or N-H indoles to 3-[p-(dialkylamino)benzyl]indoles (yield: up to 73%, conversion: up to 92%). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp3 C-H bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N-arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three-component coupling reaction of the in situ generated formaldehyde with an N-alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium-labeling experiments are consistent with the alkylation of N-alkylindoles via pathway B. The relative reaction rates of [Ru(2,6-Cl 2tpp)CO] catalyzed oxidative coupling reactions of 4-X-substituted N,N-dimethylanilines with N-phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants o (R2=0.989), giving a rho value of -1.09. This rho value and the magnitudes of the intra- and intermolecular deuterium isotope effects (kH/kD) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4-X-substituted N,N-dimethylanilines. Ruthenium-catalyzed three-component reaction of N-alkyl N-H indoles, paraformaldehyde, and anilines gave 3-[p-(dialkylamino)benzyl] indoles in up to 82% yield (conversion: up to 95%).

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

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FeCl3 in combination with t-BuOOt-Bu as an oxidant was found to catalyze oxidative coupling of alkylamines with arenes, nitroalkanes, and 1,3-dicarbonyl compounds to give arylmethylamines, beta-nitroalkylamines, and 2-(aminomethyl)-1,3-dicarbonyl compounds, respectively.

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

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A new organoplatinum(II) molecular tweezer with a stimuli-responsive 2,20:60,200-terpyridine spacer has been synthesized, which undergoes ”U”- to ”W”-shaped conformational transition upon adding Zn2+ ions. The molecular tweezer receptor displays a high binding affinity toward the complementary guests, with the implementation of Pt(II)Pt(II) metal-metal interactions for the non-covalent tweezering systems. MMLCT absorbance simultaneously emerges in the visible-light region (470-620 nm), which can be sensitized by O2 and thereby utilized for photo-catalyzed reactions in organic and aqueous media. Moreover, temporally ”on-demand” photo-catalytic efficiency can be accomplished, via the successive addition of Zn(OTf)2 and a competitive ligand to the supramolecular tweezering photosensitizers. Hence, the current study opens up new avenues toward intelligent photocatalytic materials via elaborate supramolecular engineering.

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

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Four heteroleptic copper(I) complexes containing phenanthroline and monoanionic nido-carborane-diphosphine ligands have been prepared and structurally characterized by various spectroscopic techniques and X-ray diffraction. These complexes exhibit intense absorptions in the visible range and excited-state lifetimes on the microsecond scale. Their application in visible-light-induced cross-dehydrogenative coupling reactions was investigated. Preliminary studies showed that one of the four copper(I) complexes is an efficient catalyst for photoinduced oxidative C-H functionalization using oxygen as oxidant. Furthermore, I±-functionalized tertiary amines were obtained in good-to-excellent yields by light irradiation (I» > 420 nm) of a mixture of our CuI complex, tertiary amines, and a variety of nucleophiles (nitroalkane, acetone, or indoles) under aerobic conditions. Electron paramagnetic resonance measurements provided evidence for the formation of superoxide radical anions O2-.) rather than singlet oxygen (1O2) during these photocatalytic reactions.

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

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We have developed a method for the sp3 C-H bond functionalization of tetrahydroisoquinolines (THIQs) mediated by [bis(trifluoroacetoxy)iodo]benzene (PIFA). The treatment of the THIQs with various nucleophiles in the presence of PIFA in a green solvent alternative gave the coupled products, with a C-C, C-N, or quaternary carbon center in high yields. This journal is

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An efficient oxidative Mannich reaction between tertiary amines and unmodified methyl ketones has been developed, using copper salts as the catalyst and O2 as the oxidant. The Royal Society of Chemistry 2009.

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All that glitters is gold: Highly phosphorescent gold(III) complexes (see picture) with extended pi-conjugated cyclometalating ligands exhibit rich photophysical and photochemical properties. They act as efficient photocatalysts/photosensitizers for oxidative functionalizations of secondary and tertiary benzylic amines and homogeneous hydrogen production from a water/acetonitrile mixture. Copyright

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