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Eosin y catalyzed visible light oxidative C-C and C-P bond formation

Eosin Y catalyzes efficiently the visible light mediated coupling of sp3 C-H bonds adjacent to the nitrogen atom in tetrahydroisoquinoline derivatives in the absence of an external oxidant. Nitroalkanes, dialkyl malonates, malononitrile, and dialkyl phophonates were used as pronucleophiles in this metal-free, visible light oxidative coupling reaction.

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

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Visible-Light-Driven C?H Oxidation of Cyclic Tertiary Amines: Access to Synthetic Strychnos Alkaloids with Antiviral Activity

Air and visible light have been used in facile direct C?H oxidation of cyclic tertiary amines at ambient conditions, employing organic dyes as photocatalysts and LED. Tolerance of this new environmentally compatible protocol to various side-chain derivatizations of tryptoline and tetrahydroisoquinoline substrates was demonstrated. The developed method provides a straightforward and sustainable route towards delta-lactams, which feature strong antiviral properties (EC50 down to 4.6¡À1.8 mum) against human cytomegalovirus (HCMV). The clear advantages, which are easily available and inexpensive reagents, organic dyes, visible light, air/O2 and atom efficiency, make this system highly appealing for synthesis of versatile Strychnocarpine alkaloid derivatives with antiviral activity.

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

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A cascade cross-coupling hydrogen evolution reaction by visible light catalysis

Cross-dehydrogenative-coupling reaction has long been recognized as a powerful tool to form a C-C bond directly from two different C-H bonds. Most current processes are performed by making use of stoichiometric amounts of oxidizing agents. We describe here a new type of reaction, namely cross-coupling hydrogen evolution (CCHE), with no use of any sacrificial oxidants, and only hydrogen (H2) is generated as a side product. By combining eosin Y and a graphene-supported RuO2 nanocomposite (G-RuO2) as a photosensitizer and a catalyst, the desired cross-coupling products and H 2 are achieved in quantitative yields under visible light irradiation at room temperature.

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

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Difunctionalization of the C-N Bond through tert-Butylnitrite-Initiated C-N Cleavage of 1,2,3,4-Tetrahydroisoquinolines and N, N?-Diarylimidazolidines under Transition-Metal-Free Conditions

Difunctionalization of the saturated C-N bond of 1,2,3,4-tetrahydroisoquinolines and N,N?-diarylimidazolidines was achieved using TBN as the metal-free initiator, providing a series N-nitrosoaminoaldehydes in high yields. Mechanistic study shows that the TBN-derived tBuO radical initiated the sp3 C-H bond activation, and the C-N bond cleavage was mediated by an iminium intermediate. This reaction provided a new way to cleave an inert C-N bond under mild and metal-free conditions, realizing the construction of molecular complexity through difunctionalization of the C-N bond.

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

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Transition-Metal-Free Dehydrosilylative Difluoroamidation of Tetrahydroisoquinolines under Mild Conditions

Disclosed herein is a dehydrosilylative difluoroamidation of alpha-Csp3-H of tetrahydroisoquinolines with alpha,alpha-difluoro-alpha-TMS-acetamides. The process, which occurs at ambient temperature in the absence of any transition metals, provides direct access to a broad range of alpha,alpha-difluoroacetamide-substituted tertiary amine derivatives in high yields. Moreover, the method was successfully applied in the Csp3-H-directed difluorophosphorylation and difluorocarboxylation under the same conditions.

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

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Gold-complexes catalyzed oxidative alpha-cyanation of tertiary amines

Oxidative alpha-cyanation of tertiary amines is catalyzed by gold complexes with trimethylsilyl cyanide to afford the corresponding alpha-aminonitriles in the presence of tert-butyl hydroperoxide in good to excellent yields under acid-free conditions at room temperature.

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

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Dual C-H functionalization of N-aryl tetrahydroisoquinolines: A highly diastereoselective synthesis of dibenzo[a,f]quinolizines via visible-light induced oxidation and inverse electron-demand aza-Diels-Alder reaction

Described herein is the first example of the application of an iminium intermediate generated by visible-light photocatalyzed oxidation in an inverse electron-demand aza-Diels-Alder reaction. This dual functionalization of both C(sp3)-H and C(sp2)-H bonds of N-aryl tetrahydroisoquinolines represents a valuable example for access to polycycles with high diastereoselectivity.

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

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Luminescent organogold(III) complexes with long-lived triplet excited states for light-induced oxidative C-H bond functionalization and hydrogen production

All that glitters is gold: Highly phosphorescent gold(III) complexes (see picture) with extended pi-conjugated cyclometalating ligands exhibit rich photophysical and photochemical properties. They act as efficient photocatalysts/photosensitizers for oxidative functionalizations of secondary and tertiary benzylic amines and homogeneous hydrogen production from a water/acetonitrile mixture. Copyright

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

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Monofluoromethylation of tetrahydroisoquinolines by visible-light induced direct C(sp3)-H bond activation

A visible-light photoredox-catalyzed reaction of tetrahydroisoquinolines with beta-fluorinated gem-diols results in the formation of C1-monofluoromethylated tetrahydroisoquinolines via C(sp3)-H bond activation. This protocol provides a new method to introduce a CF group with stable, easily-prepared monofluorinated gem-diol as CF source. A mechanistic investigation is presented based on control experiments.

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

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Highly efficient aerobic ruthenium-catalyzed oxidative cross-dehydrogenative coupling for sp3-sp3 carbon-carbon bond formation

A highly efficient sp3-sp3 carbon-carbon bond formation system was developed for the aerobic ruthenium-catalyzed oxidative cross-dehydrogenative coupling reaction between tertiary amines and sp3 C-H compounds in the presence of RuCl3/O2, thus giving the corresponding alpha-functionalized amines. Compared with the reported method, H2O2 or tBuOOH was replaced successfully by economical and facile oxygen as the oxidant. Three types of activated C-H bonds for pronucleophiles were evaluated in this system. All these features combined are in accordance with important prospective green chemistry aspects.

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