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

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A simple and effective catalytic method to construct propargylamine was developed by using copper bromide and tert-BuOOH via a combination of sp3 C-H bond and sp C-H bond activations followed by C-C bond formation. Copyright

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

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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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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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Structural modification of the tetrahydroisoquinoline (THIQ) framework is of significant interest to organic chemists due to its central role in heterocyclic and medicinal chemistry. Here we demonstrate an efficient metal-free method for the oxidative functionalization of THIQs at the C1 position, which is amenable to a diverse range of C-C coupling reactions. These reactions proceed through a hydride abstraction involving the tropylium ion followed by quenching the generated iminium intermediates with nucleophiles to afford THIQ derivatives with excellent efficiencies and interesting selectivities.

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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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With visible-light irradiation, a mild, simple, and efficient metal-free photocatalytic system for the facile construction of sp3-sp 3 C-C bonds between tertiary amines and activated C-H bonds has been achieved. Spectroscopic study and product analysis demonstrate for the first time that photoinduced electron transfer from N-aryl tetrahydroisoquinolines to eosin Y bis(tetrabutylammonium salt) (TBA-eosin Y) takes place to generate TBA-eosin Y radical anion, which can subsequently react with nucleophiles and molecular oxygen. More strikingly, electron spin resonance (ESR) measurements provide direct evidence for the formation of superoxide radical anions (O 2) rather than singlet oxygen (1O 2) during visible-light irradiation. This active species is therefore believed to be responsible for the large rate of acceleration of the aerobic photocatalytic reactions. Light work: With visible-light irradiation (lambda>450 nm), a mild, simple and efficient metal-free photocatalytic system for the facile construction of sp3-sp3 C-C bonds between tertiary amines and activated C-H bonds has been achieved (see scheme). Electron spin resonance measurements offer direct evidence for the formation of superoxide radical anions (O2) during visible-light irradiation. Copyright

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Tetrahydroisoquinoline – Wikipedia,
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Within the last couple of years, the photocatalytic, oxidative C-C coupling has grown to a well-established methodology, especially for the modification of aryl-substituted tetrahydroisoquinoline derivatives. However, until now, this reaction is mainly restricted to the usage of strong nucleophiles like nitroalkanes, cyanides, enamines, phosphonates and malonates. Within this publication we present an extension of such a method towards the application of weaker nucleophiles, namely allylstannanes, allylsilanes and allylboranes. Therefore, a very simple protocol was invented, using heterogeneous mesoporous graphitic carbon nitride (mpg-C3N4) as catalyst and air as oxidizing agent, leading to high yields for a broad range of substrates.

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Cyclic tertiary amines can be oxidatively coupled with a variety of silyl enol ethers or ketene acetals to furnish tertiary Mannich bases. The reactions are catalyzed by simple copper salts employing elemental oxygen as the oxidant. Georg Thieme Verlag Stuttgart.

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Tetrahydroisoquinoline – Wikipedia,
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N-aryl 1,2,3,4-tetrahydroisoquinolines were prepared rapidly in good yields by the microwave-assisted Pd-catalysed coupling of (hetero)aryl iodides or bromides with 1,2,3,4-tetrahydroisoquinoline. Reactions were typically complete within 5 min for aryl iodides and within 30 min for pyridyl bromides.

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Reference:
Tetrahydroisoquinoline – Wikipedia,
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