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Metal nanoparticles supported on two-dimensional graphenes as heterogeneous catalysts

The catalytic activity of metal nanoparticles (MNPs) is highly dependent on the nature of the support. In addition to the role of particle size stabilization in decreasing the spontaneous growth of small MNPs, the main role of the support is to cooperate by providing efficient pathways that lead to the target product. Thus, the necessary requirements for supports include a large surface area, strong metal-support interaction, and the presence of active sites that participate in the reaction mechanism. Active carbons as well as organic polymers and large surface area inorganic metal oxides are typical insoluble solids that are used frequently as supports. Furthermore, the recent availability of suspensions of graphene oxide (GO), reduced GO, and other graphene-based materials (Gs) has provided new opportunities for the development of supported MNPs as catalysts. As supports, Gs combine several useful properties that are not encountered in classical solid supports. Gs comprise sheets that are a single carbon atom in thickness, which approaches the physical limit for a two-dimensional (2D) surface in which MNPs can be deposited. Therefore, Gs are among the solids with the highest possible surface area and due to their single layer morphology, they are readily dispersed in a liquid phase with the appearance of homogeneous catalyst, but they are easily recovered by filtration or centrifugation. In addition, Gs may cooperate with the catalytic cycle involving MNPs in at least four distinctive ways: (i) by strong adsorption of the substrates and reagents near the MNP; (ii) via d-pi metal support interaction, which influences the electron density of the MNP; (iii) promoting substrate reactivity by giving or withdrawing the electron density from the substrate; and (iv) by making specific catalytic sites available on the G nanosheet due to defects, oxygenated functional groups, or the presence of dopants. This review highlights the specific features derived from the morphology and characteristics of Gs, as well as the different catalytic behaviors of G-supported MNPs compared with related catalysts. One of the aims of this review is to provide a reference to indicate best practices as well as suggesting benchmark reactions to evaluate the catalytic activity of different materials. Considering the growth in the use of G as supports and the unique features obtained by employing 2D Gs as supports for MNPs, the present review has implications in the fields of catalysis, biocatalysis, and material science.

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

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Dual C-H functionalization of N-aryl amines: Synthesis of polycyclic amines via an oxidative povarov approach

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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Robust Buchwald-Hartwig amination enabled by ball-milling

An operationally simple mechanochemical method for the Pd catalysed Buchwald-Hartwig amination of arylhalides with secondary amines has been developed using a Pd PEPPSI catalyst system. The system is demonstrated on 30 substrates and applied in the context of a target synthesis. Furthermore, the performance of the reaction under aerobic conditions has been probed under traditional solution and mechanochemical conditions, the observations are discussed herein.

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

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Palladium in Photocatalysis

The concept of photoredox/transition-metal dual catalysis has been validated as a powerful platform for the construction of carbon-carbon and carbon-heteroatom bonds, and it illustrates the power of rational design in catalysis and the strategic use of mechanistic knowledge and manipulation for the development of novel synthetic methods. This chapter describes recent progress in the combination of visible-light photoredox catalysis with palladium catalysis, highlighting this as a valuable synthetic tool in accessing complex molecules in a rapid and modular fashion.

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Synthesis of 3-Benzazepines by Metal-Free Oxidative C?H Bond Functionalization?Ring Expansion Tandem Reaction

A metal-free synthesis of biologically important benzazepines is achieved through a single synthetic operation involving an oxidative C?H bond functionalization and ring expansion with diazomethanes as key reagent. This represents a new, strong methodology for the straightforward construction of the seven-ring N-heterocyclic structures under mild conditions using a 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) oxoammonium salt as oxidant. Moderate to good yields are achieved from simple, readily available tetrahydroisoquinolines, and this methodology has been further successfully applied for the synthesis of the 3-benzazepine drug Lorcaserin. A possible mechanistic pathway for the ring expansion step, comprising the extrusion of nitrogen in a concerted asynchronic process, is proposed based on both mechanistic proof and density function theory (DFT) calculations. (Figure presented.).

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

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Transition metal-free alpha-C(sp3)-H bond functionalization of amines by oxidative cross dehydrogenative coupling reaction: Simple and direct access to C-4-alkylated 3,4-dihydroquinazoline derivatives

A transition metal-free catalytic system has been developed for the cross dehydrogenative coupling of amines with nitroalkanes under mild condition employing potassium iodide/tert-butyl hydrogen peroxide catalytic system. This methodology was further extended for the construction of biologically important N-heterocycles, namely, 3,4-dihydroquinazoline derivatives. This novel strategy provides a simple, efficient, and direct access to 4-alkyl-3,4- dihydroquinazoline derivatives. Copyright

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Tetrahydroisoquinoline – Wikipedia,
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Cross-dehydrogenative C(sp3)-C(sp3) coupling: Via C-H activation using magnetically retrievable ruthenium-based photoredox nanocatalyst under aerobic conditions

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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Bronsted acid cocatalysts in photocatalytic radical addition of alpha-amino C-H bonds across michael acceptors

In marked contrast to the variety of strategies available for oxidation and nucleophilic functionalization of methylene groups adjacent to amines, relatively few approaches for modification of this position with electrophilic reaction partners have been reported. In the course of an investigation of the reactions of photogenerated alpha-amino radicals with electrophiles, we made the surprising observation that the efficiency of radical photoredox functionalization of N-aryl tetrahydroisoquinolines is dramatically increased in the presence of a Bronsted acid cocatalyst. Optimized conditions provide high yields and efficient conversion to radical addition products for a range of structurally modified tetrahydroisoquinolines and enones using convenient household light sources and commercially available Ru(bpy)3Cl 2 as a photocatalyst. Our investigations into the origins of this unexpected additive effect have demonstrated that the carbon-carbon bond-forming step is accelerated by TFA and is a rare example of Bronsted acid catalysis in radical addition reactions. Moreover, a significant conclusion arising from these studies is the finding that product formation is dominated by radical chain processes and not by photocatalyst turnover. Together, these findings have important implications for the future design and mechanistic evaluation of photocatalytic radical processses.

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

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Application of microflow conditions to visible light photoredox catalysis

Applications of microflow conditions for visible light photoredox catalysis have successfully been developed. Operationally simple microreactor and FEP (fluorinated ethylene propylene copolymer) tube reactor systems enable significant improvement of several photoredox reactions using different photocatalysts such as [Ru(bpy)3]2+ and Eosin Y. Apart from rate acceleration, this approach facilitates previously challenging transformations of nonstabilized intermediates. Additionally, the productivity of the synergistic, catalytic enantioselective photoredox alpha-alkylation of aldehydes was demonstrated to be increased by 2 orders of magnitude.

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Tetrahydroisoquinoline – Wikipedia,
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Catalytic amounts of triarylaminium salt initiated aerobic oxidative coupling of N-aryl tetrahydroisoquinolines

A novel stable radical cation triarylaminium salt able to induce aerobic oxidative alpha-C-H functionalization of tertiary amines in catalytic amounts has been developed. The reaction is performed in the absence of any other additives under mild conditions and only requires atmosphere air as a sustainable co-oxidant.

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