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Visible-light induced enhancement in the multi-catalytic activity of sulfated carbon dots for aerobic carbon-carbon bond formation

The development of carbonaceous materials as metal-free catalysts integrating different types of catalysis in a single system represents a significant advance in cascade/tandem organic synthesis. Zero-dimensional carbon dots with tuneable optical properties and easily modifiable surface functionalities can be harnessed as a carbocatalyst for merging photooxidation and acid-catalyzed reactions in one pot. Herein, we explore carbon dots decorated with hydrogen sulfate groups as a photocatalyst for the dehydrogenative cross-coupling of xanthenes with ketones, arenes and 1,3-dicarbonyl compounds that showed high efficiency and selectivity under visible-light irradiation. The sulphated carbon dots demonstrate dual catalytic properties, wherein they induced the rapid photooxidation of xanthenes in the presence of molecular oxygen to form a hydroperoxy intermediate followed by coupling of nucleophiles catalysed by the acidic surface functional groups. The methodology represents an operationally simple pathway for the generation of C-C coupling products in a short reaction time with wide substrate scopes under mild conditions. The catalyst is easily separable and can be reused over multiple cycles with good efficiency.

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

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Cross-dehydrogenative coupling reaction using copper oxide impregnated on magnetite in deep eutectic solvents

The synthesis of different tetrahydroisoquinolines using choline chlorideethylene glycol as a deep eutectic solvent (DES) and copper(ii) oxide impregnated on magnetite as a catalyst has been accomplished successfully. The copper catalyst amount is the lowest loading ever reported. The presence of DES showed to be essential since the reaction in the absence of this medium did not proceed. A direct proportional relationship was found between the conductivity of DES medium and the yield obtained. The DES and the catalyst could be reused up to ten times without any detrimental effect on the yield of the reaction, with the aerobic conditions making the protocol highly sustainable, where the only waste is water.

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

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Three-Component Coupling Involving Arynes, Aromatic Tertiary Amines, and Aldehydes via Aryl-Aryl Amino Group Migration

The transition-metal-free multicomponent coupling of arynes, aromatic tertiary amines, and aldehydes proceeding via the aryl to aryl amino group migration has been demonstrated. This protocol allows rapid access to ortho-functionalized tertiary amines in moderate to good yields. Moreover, activated ketones can also be used as the aldehyde component in the present reaction. The similarity of the aryl-aryl tertiary amino group migration with the Smiles rearrangement is striking.

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

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alpha-Alkylation of tertiary amines by C(sp3)?C(sp3) cross-coupling under redox neutral photocatalysis

Direct alpha-alkylation of N-phenyl-tetrahydroisoquinoline with alkyl selenides of desired alkyl chain length and functionality is reported by photoredox catalysis. Construction of hexahydro pyrrolo- and pyrido-isoquinoline scaffolds along with indolines and tetrahydroquinolines is also described by intramolecular C(sp3)?C(sp3) cross-couplings.

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

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Solvent-free cross-dehydrogenative coupling reactions under high speed ball-milling conditions applied to the synthesis of functionalized tetrahydroisoquinolines

Solvent-free reaction using a high-speed ball milling technique has been first applied to cross-dehydrogenative coupling (CDC) reactions between tetrahydroisoquinolines and three types of pronucleophiles such as nitroalkanes, alkynes, and indoles. All coupling products were obtained in good yields at short reaction times (no more than 40 min). When alkynes and indoles were used as pronucleophile, the reactions can be catalyzed efficiently by recoverable copper balls without any additional metal catalyst.

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

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Merging of the photocatalysis and copper catalysis in metal-organic frameworks for oxidative C-C bond formation

The direct formation of new C-C bonds through photocatalytic oxidative coupling from low reactive sp3 C-H bonds using environmentally benign and cheap oxygen as oxidant is an important area in sustainable chemistry. By incorporating the photoredox catalyst [SiW11O39Ru(H2O)]5- into the pores of Cu-based metal-organic frameworks, a new approach for merging Cu-catalysis/Ru-photocatalysis within one single MOF was achieved. The direct CuII-O-W(Ru) bridges made the two metal catalyses being synergetic, enabling the application on the catalysis of the oxidative coupling C-C bond formation from acetophenones and N-phenyl-tetrahydroisoquinoline with excellent conversion and size-selectivity. The method takes advantage of visible light photoredox catalysis to generate iminium ion intermediate from N-phenyl-tetrahydroisoquinoline under mild conditions and the easy combination with Cu-catalyzed activation of nucleophiles. Control catalytic experiments using similar Cu-based sheets but with the photoredox catalytic anions embedded was also investigated for comparison.

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

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Iron-catalyzed oxidative coupling of alkylamines with arenes, nitroalkanes, and 1,3-dicarbonyl compounds

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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Synthesis of N-aryl substituted, five- and six-membered azacycles using aluminum-amide complexes

Synthesis of N-aryl substituted, five- and six-membered azacycloalkanes, isoindolines and tetrahydroisoquinolines, has been described. In this synthesis, cyclic ethers (n = 1, 2) were treated with dimethylaluminum-amide reagents, derived from a range of aryl amines and trimethylaluminum, to afford the corresponding azacycles in good yields. This journal is the Partner Organisations 2014.

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

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Photocatalytic deaminative benzylation and alkylation of tetrahydroisoquinolines with N-alkylpyrydinium salts

A ruthenium-catalyzed photoredox coupling of substituted N-aryltetrahydroisoquinolines (THIQs) and different bench-stable pyridinium salts was successfully developed to give fast access to 1-benzyl-THIQs. Furthermore, secondary alkyl and allyl groups were also successfully introduced via the same method. Additionally, the typically applied N-phenyl group in the THIQ substrate could be replaced by the cleavable p-methoxyphenyl (PMP) group and successful N-deprotection was demonstrated.

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

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Iron catalyzed oxidative cyanation of tertiary amines

Iron(ii) and iron(iii) salts catalyze the oxidative alpha-cyanation of tertiary amines by trimethylsilyl cyanide in the presence of tert-butylhydroperoxide under acid-free conditions at room temperature.

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