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Radical alkylation of C(sp3)-H bonds with diacyl peroxides under catalyst-free conditions

Herein, we describe a protocol for alkylation reactions of C(sp3)-H bonds with diacyl peroxides by means of a process involving cross-coupling between an alkyl radical and an alpha-Aminoalkyl radical. The mild, catalyst-And additive-free conditions make this protocol superior to previously reported C(sp3)-H alkylation strategies. The protocol was applied to 1,2,3,4-Tetrahydroisoquinolines and a tetrahydro-beta-carboline derivative and could be carried out on a gram scale, indicating its utility for the alkylation of late-stage synthetic intermediates.

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

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Thieme Chemistry Journal Awardees – Where are they now? Aerobic oxidative coupling of tertiary amines with silyl enolates and ketene acetals

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

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alpha-Cyanation of Aromatic Tertiary Amines using Ferricyanide as a Non-Toxic Cyanide Source

The reaction of aromatic tertiary amines with potassium ferricyanide directly provides the useful alpha-amino nitriles. The inexpensive iron complex functions both as an oxidant and as a cyanide source. The presence of molecular oxygen speeds up the reaction which can be performed in aqueous tert-butanol or even in ethanol-based mixtures like Tequila. While amine cyanations usually employ highly toxic cyanide sources, potassium ferricyanide is even less toxic than table salt. No expensive metal complexes are required as catalysts and the co-product of the cyanation, Prussian blue, has no known toxicity and is rather used as an antidote.

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

The Absolute Best Science Experiment for 2-Phenyl-1,2,3,4-tetrahydroisoquinoline

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Light-mediated heterogeneous cross dehydrogenative coupling reactions: Metal oxides as efficient, recyclable, photoredox catalysts in C-C bond-forming reactions

Let there be light: A heterogeneous photocatalytic system based on easily recyclable TiO2 or ZnO allows cross dehydrogenative coupling reactions of tertiary amines. The newly developed protocols have successfully been applied to various C-C and C-P bond-forming reactions to provide nitro amines as well as amino ketones, nitriles and phosphonates. Copyright

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

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Metal-Free Synthesis of alpha-Aminophosphonates from Tertiary Amines and P(O)H Compounds via a Cross-Dehydrogenative Coupling Reaction

The various alpha-aminophosphonates have been prepared from tertiary aromatic and aliphatic amines with P(O)H compounds via a tert -butyl hydroperoxide mediated cross-dehydrogenative coupling reaction, eliminating the need for transition-metal catalysts. The oxidation of tertiary amine by tert -butyl hydroperoxide generates an iminium cation intermediate. A further addition of P(O)H compound to iminium cation gives the desired product.

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

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Molecular iodine catalyzed cross-dehydrogenative coupling reaction between two sp3 C-H bonds using hydrogen peroxide

A useful method for molecular iodine catalyzed oxidative C-C bond formation between tertiary amines and a carbon nucleophile using hydrogen peroxide as the terminal oxidant is reported. This is the first report of a molecular iodine catalyzed cross-dehydrogenative coupling (CDC) reaction between two sp 3 C-H bonds.

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Synthesis and reactivity of pentavalent biphenyl-2,2?-ylenebismuth derivatives

Phenylbiphenyl-2,2?-ylenebismuth diacetate reacted with nucleophiles under basic conditions to give modest to good yields of the C-phenylated substrates. Under copper catalysis, it reacted with hydroxy or amino groups to give the products of O- or N-phenylation. In both sets of reaction conditions, this reagent showed a reduced reactivity compared to the analogous triphenylbismuth diacetate reagent. It showed also a high regioselectivity as only the phenyl derivatives were detected and isolated. The Royal Society of Chemistry 2000.

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

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Gold(I)-catalyzed synthesis of dihydrodibenzoquinolizinium salts

A gold-catalyzed cyclization of 1-alkynyl-2-aryl tetrahydroisoquinolines is described for the synthesis of novel dihydrodibenzoquinolizinium salts. The reaction mechanism is likely to involve a 6-endo-dig cyclization and subsequent oxidation by air to give a relatively stable arylgold intermediate. This gold species undergoes protodeauration under acidic conditions to afford the title compounds. An NMR study was performed to gain further evidence and insight on the presence of the arylgold intermediate and the reaction mechanism. (Figure presented.).

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

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Visible-light-induced direct C(sp3)-H difluromethylation of tetrahydroisoquinolines with the in situ generated difluoroenolates

An effective approach to C1-difluoromethylated tetrahydroisoquinoline derivatives has been developed through C-H functionalization of tertiary amines by visible-light photoredox catalysis. This method uses stable, easily obtained alpha,alpha-difluorinated gem-diol as the CF2 source. The corresponding products were obtained in moderate to high yields at ambient temperature. the Partner Organisations 2014.

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

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Tetrabutylammonium Bromide-Promoted Metal-Free, Efficient, Rapid, and Scalable Synthesis of N-Aryl Amines

A rapid, transition metal-free, high-yielding, tetrabutylammonium bromide-promoted method of N-arylation is reported within. The optimized conditions tolerated a wide range of secondary amines and was equally effective with bromo- and chlorobenzene-including substituted aryl halides. The developed method is found to be effective for N-arylation when compared to earlier methods which involve harsh conditions, transition metals, lack of scalability, and long reaction times. Our method utilizes conventional heating only; it is readily scalable; and the products are facile to purify.

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