The important role of 2-Phenyl-1,2,3,4-tetrahydroisoquinoline

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The cross-dehydrogenative coupling (CDC) reaction of N-aryltetrahydroisoquinolines (THIQ) is one of the most exploited photocatalytic transformation and a test reaction for an exceptional variety of catalysts. However, its mechanism remained unclear concerning involved intermediates, reactive pathways of the amine radical cation and the influence of oxygen and the light source. Therefore, nuclear magnetic resonance (NMR), electron spin resonance (ESR) and synthetic methods were combined to provide a comprehensive picture of the reaction mechanism using Ru(bpy)3Cl2 as a photocatalyst under aerobic and anaerobic conditions. The reaction profiles and involved intermediates were monitored and analyzed by NMR spectroscopy. Several intermediates contributing to product formation were identified, the iminium ion, the hydroperoxide and dimer of THIQ, and a new ring opened intermediate, cleaved at the benzylic C-N bond. Mechanistic evidence is given that under anaerobic conditions preferentially the alpha-amino radical is formed by deprotonation, in contrast to the formation of iminium ions via H?-abstraction in the presence of oxygen. Further, the light-induced background reaction in the absence of the catalyst was studied in detail, revealing that the product formation rate is correlated to the intensity and wavelength of the light source and that oxygen is essential for an efficient conversion. The reaction rate and efficiency is comparable to previously reported photocatalytic systems, performed under aerobic conditions in combination with intense blue light sources. Thus, the multitude of reaction parameters investigated reveals the preference for hydrogen atom or proton abstraction in photoreactions and allows to assess the influence of experimental conditions on the mechanistic pathways.

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

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A mechanochemical oxidative Mannich reaction of N-tert-butoxycarbonyl (Boc) tetrahydroquinolines and ketones was successfully developed under solvent-free ball-milling conditions. The reaction afforded the desired coupling products in satisfactory yields under mild and tractable oxidative conditions. Side reactions such as deprotection of the Boc group were prevented by carefully adjusting the milling parameters, including milling frequency, time, milling-ball filling degree, milling-ball size, and grinding auxiliary. Further examination of the scope indicated that the reaction system could also be applied to the N-benzyloxycarbonyl and N-aryl substrates to afford the corresponding products in moderate to good yields.

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

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Aerobic oxidation reaction of amines to imines catalyzed by polymer-incarcerated Au nanoclusters (PI-Au) was developed. The effect of cluster size for this oxidation reaction was carefully examined using the same polymer support. We have succeeded in preparation of various PI-Au catalysts containing different size clusters by modification of standard preparation methods. The size of clusters and their distribution were analyzed by electron microscopy. Interestingly, catalysts containing relatively larger clusters (>5 nm) showed higher activity in aerobic oxidation of amines than catalysts containing smaller clusters (13 nm) that showed much better activity for aerobic oxidation of alcohols. In addition, novel Au nanocluster catalysts immobilized on newly prepared polymer with tertiary amine groups were developed and they showed excellent activity for aerobic oxidation of amines to imines. The relation between cluster size and catalytic activity and role of tertiary amine in polymer were discussed. These catalysts could be applied to aerobic oxidative deprotection of p-methoxybenzyl groups.

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

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(Chemical Equation Presented) An efficient method was developed for arylation of sp3 C-H bonds using copper bromide as catalyst in absence of directing group with arylboronic acids. The oxidative arylation provides easy access to biologically active tetrahydroisoquinoline derivatives and can either use peroxide or molecular oxygen as oxidant.

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

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A porous polymer containing a fluorophenylphenanthroimidazole core was easily prepared via one-pot Suzuki-Miyaura cross-coupling reactions under microwave heating. These new metal-free polymers have demonstrated heterogeneous photocatalytic activity toward aza-Henry reaction with reasonable recyclability. Their preparation require a minimal workup to build porous networks with control over the apparent surface area and pore volume from suitable molecular building blocks containing 2-(1H-phenanthro[9,10-d]imidazol-2-yl)-3,5-difluorophenol (PhIm-2F), as rigid and multitopic node, which afforded a conjugated porous polymer (CPP-PhIm-2F). A series of fluorinated ligands have shown their capability in the preparation of soluble and supported cationic Ru(bpy)2(F-phenanthroimidazole) complexes by reaction with Ru(bpy)2Cl2 and demonstrating a beneficial effect of two fluorine atoms on the photocatalytic effect.

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

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A cross-dehydrogenative coupling (CDC) reaction between tertiary amines and nitroalkanes has been realized under an oxygen atmosphere in water simply by using graphene-supported RuO2 as the catalyst, which was made from water-soluble graphene with sulfonic groups and RuCl3·nH 2O to form RuO2·nH2O nanocomposites in situ. In contrast to RuCl3·nH2O and RuO 2·nH2O, the graphene-supported RuO2 nanoparticles exhibited higher activity and stability for the aerobic CDC reaction in water.

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

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The present invention relates to a 2,9-dimethyl -4,7-diphenyl -1,10-O-phenanthrene carborane double-phenyl a phosphine price copper complexes in the visible light catalytic 2-methyl quinoline compounds with tetrahydroisoquinoline compound dehydrogenation method of coupling reaction. The preparation method of this invention is: the photocatalyst 2,9-dimethyl -4,7-diphenyl -1,10-O-phenanthrene carborane double-phenyl a phosphine price copper complex, the corresponding 2-methyl quinoline, tetrahydroisoquinoline and inter-methyl benzoic acid according to 0.015: 2:1:3 molar ratio of mixing, adding solvent acetonitrile and methanol, acetonitrile and methanol in accordance with the 1:1 volume ratio of mixing, the reaction system is filled with oxygen, mercury distance of 2 cm is at 3.5w white light of the lamp strip led, in 35 hours later, the solvent out of the reaction system, through the silica gel column chromatography separation, to obtain the corresponding product. The beneficial effect of this method for the use of visible photocatalytic reaction, environmental protection and low carbon. (by machine translation)

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

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Iminium ions generated in situ via copper(I) bromide catalyzed oxidation of N-aryl amines readily undergo [4 + 2] cycloadditions with a range of dienophiles. This method involves the functionalization of both a C(sp 3)-H and a C(sp2)-H bond and enables the rapid construction of polycyclic amines under relatively mild conditions.

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

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A novel method for the synthesis of cyanomethylated tetrahydroisoquinolines has been developed with mild reaction conditions, good yields and a broad substrate scope. Acetonitrile, a common solvent, is for the first time used as a pronucleophile for this type of two sp3C?H bonds cross-dehydrogenative coupling (CDC) reaction. A new oxidative system (CuCl2/TEMPO/Cs2CO3) has been established by our group, in which the mild TEMPO reagent was found to be a highly efficient oxidant. (Figure presented.).

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

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A photoredox-catalyzed umpolung strategy for coupling reactions between aldehydes, ketones, imines, and N-arylamines is reported. These reactions proceed by a Br°nsted acid-activated proton-coupled electron transfer pathway, and the protocol was used to synthesize a broad scope of 1,2-amino alcohols and vicinal diamines, both of which are common motifs in biologically active natural products, pharmaceutically active molecules, and ligands.

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