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Metal-free visible-light induced cross-dehydrogenative coupling of tertiary amines with diazo compounds

The first visible-light induced cross-dehydrogenative coupling between tertiary amines and diazo compounds is described. The reaction proceeds smoothly under mild and metal-free conditions by using air or O2 as the oxidant, affording various beta-amino-alpha-diazo adducts in moderate to good yields with broad substrate scopes. The resulting products were successfully employed for the synthesis of 4- or 5-ester N-aryl-2,3- dihydrobenzo[d]azepines with high regioselectivity simply switched by the selection of the transition metal catalysts.

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

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Efficient visible light-mediated cross-dehydrogenative coupling reactions of tertiary amines catalyzed by a polymer-immobilized iridium-based photocatalyst

The immobilization of an iridium-based heterogeneous photocatalyst via a radical polymerization process is described, and its catalytic activity was evaluated for the aerobic phosphonylation reaction of N-aryl tetrahydroisoquinolines under visible light irradiation. the Partner Organisations 2014.

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

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Aerobic oxidation of amines catalyzed by polymer-incarcerated au nanoclusters: Effect of cluster size and cooperative functional groups in the polymer

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

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Photoredox activation and anion binding catalysis in the dual catalytic enantioselective synthesis of beta-amino esters

The enantioselective oxidative C-H functionalization of tetrahydroisoquinoline derivatives is achieved through the merger of photoredox and asymmetric anion-binding catalysis. This combination of two distinct catalysis concepts introduces a potentially general approach to asymmetric transformations in oxidative photocatalysis.

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

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Visible-Light-Mediated Efficient Metal-Free Catalyst for alpha-Oxygenation of Tertiary Amines to Amides

A metal-free system has been discovered for the efficient alpha-oxygenation of tertiary amines to the corresponding amides using oxygen as an oxidant. This visible-light-mediated oxygenation reaction exhibited excellent substrates scope under mild reaction conditions and generated water as the only byproduct. The synthetic utility of this approach has been demonstrated by applying onto drug molecules. At the end, detailed mechanistic reactions clearly showed the role of oxygen and the photocatalyst.

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

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N-Aryl Groups Are Ubiquitous in Cross-Dehydrogenative Couplings Because They Stabilize Reactive Intermediates

The mechanism of cross-dehydrogenative coupling (CDC) reactions has been examined by experimental and computational methods. We provide a rationale for the ubiquity of the N-aryl group in these reactions. The aryl substituent stabilizes two intermediates and the high-energy transition state that connects them, which together represent the rate-determining step. This knowledge has enabled us to predict whether new CDC substrates will react either well or poorly.

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

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Direct sp3 C-H bond arylation, alkylation, and amidation of tetrahydroisoquinolines mediated by hypervalent iodine(iii) under mild conditions

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

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Organocatalyzed asymmetric oxidative coupling of alpha-Csp3-H of tertiary amines to alpha,beta-unsaturated gamma-butyrolactam: Synthesis of MBH-type products

A unique organocatalytic asymmetric oxidative cross-dehydrogenative coupling of a alpha-Csp3-H bond of tertiary amines with alpha,beta-unsaturated gamma-butyrolactams to generate Morita-Baylis-Hillman-type products has been realized for the first time. This method provides an efficient way to access a series of alpha-heterocyclic optically active tetrahydroisoquinoline scaffolds. (Chemical Equation Presented).

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

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Oxidative alpha-Trichloromethylation of Tertiary Amines: An Entry to alpha-Amino Acid Esters

alpha-Trichloromethylation of tertiary amines with trimethyl(trichloromethyl)silane by oxidative coupling, using DDQ as an oxidant, has been realized. The reaction is instantaneous, is scalable, and tolerates a broad range of functional groups and heteroarenes. The trichloromethylated products can be easily converted into beta,beta-dichloroamines, enamines, and alpha-amino acid esters under operationally simple conditions. This methodology provides an efficient alternative to the poisonous cyanation reactions for the synthesis of carboxylic acid and their derivatives.

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

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WO3 nanospheres with improved catalytic activity for visible light induced cross dehydrogenative coupling reactions

Three tungsten oxides (WO3-W1 to WO3-W3) with different morphologies were prepared and characterized by XRD, SEM, TEM and HR-TEM measurements. The as-synthesized tungsten oxides were screened as photocatalysts for visible-light-driven cross dehydrogenative coupling (CDC) reactions along with commercially available WO3-W4. Preliminary studies showed that WO3-W1 with hollow sphere morphology efficiently photocatalyzed oxidative C?H functionalization as compared to other tested samples, by using molecular oxygen as a benign oxidant. The superior photocatalytic performance of WO3-W1 can be attributed to its larger surface area and pore structure which was supported by nitrogen adsorption-desorption measurements. Further, this protocol was used to synthesize alpha-functionalized tertiary amines in good to excellent yields by irradiating a mixture of WO3-W1, tertiary amine, and nucleophiles (nitromethane or ketones) to visible light under aerobic conditions. Moreover, WO3-W1 can be recycled and reused with no obvious change in catalytic activity, indicating that this is an environmentally friendly and economical protocol and also underlines the robustness of the catalysts in light mediated cross dehydrogenative coupling reactions. It is hoped that our results could offer useful information for designing of new heterogeneous semiconductors for photoredox catalytic organic reactions.

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