55653-99-1

Upstream product

• 1239-56-1 1-(2,3-diphenyl-1H-indol-1-yl)ethan-1-one 
• 119-53-9 2-hydroxy-2-phenylacetophenone 
• 103-69-5 N-ethyl-N-phenylamine 
• 826-42-6 N,N-diethylaniline N-oxide 
• 501-65-5 diphenyl acetylene 
• 825-19-4 N-methyl-N-ethylaniline N-oxide 
• 74-96-4 ethyl bromide 
• 3469-20-3 2,3-diphenyl-1H-indole 
• 62-53-3 aniline 
• 612-64-6 N-ethyl-N-nitrosoaniline 
• 886-38-4 diphenylcyclopropenone 
• 615-43-0 2-iodophenylamine 
• 110-89-4 piperidine 
• 1529541-83-0 2-iodo-N,N-diethylaniline 

Relevant academic research and scientific papers

One-Pot Tandem ortho-Naphthoquinone-Catalyzed Aerobic Nitrosation of N-Alkylanilines and Rh(III)-Catalyzed C-H Functionalization Sequence to Indole and Aniline Derivatives

The nitroso group served as a traceless directing group for the C-H functionalization of N-alkylanilines, ultimately removed after functioning either as an internal oxidant or under subsequent reducing conditions. The unique ability of o-NQ catalysts to aerobically oxidize the N-alkylanilines without using solvents and stoichiometric amounts of oxidants has rendered the new opportunity to develop the telescoped catalyst systems without a need for directly handling the hazardous N-nitroso compounds.

Divergent C-H activation synthesis of chalcones, quinolones and indoles

We here report a condition-controlled divergent synthesis strategy of chalcones, quinolones and indoles, which was achieved via a C-H activation reaction of N-nitrosoanilines and cyclopropenones. Variations of Ag salts are observed to be crucial for divergently constructing the three distinct chemical scaffolds. A Rh(i)- and Rh(iii)-cocatalyzed decarbonylation/C-H activation/[3+2] annulation cascade reaction was developed for the synthesis of indoles. These methodologies are characterized by mild reaction conditions, high functional group tolerance, and amenability to gram-scale synthesis, providing a reference for future derivation of new chemical scaffolds by C-H activation.

Predicting the Outcome of Photocyclisation Reactions: A Joint Experimental and Computational Investigation

Photochemical oxidative cyclodehydrogenation reactions are a versatile class of aromatic ring-forming reactions. They are tolerant to functional group substitution and heteroatom inclusion, so can be used to form a diverse range of extended polyaromatic systems by fusing existing ring substituents. However, despite their undoubted synthetic utility, there are no existing models—computational or heuristic—that predict the outcome of photocyclisation reactions across all possible classes of reactants. This can be traced back to the fact that “negative” results are rarely published in the synthetic literature and the lack of a general conceptual framework for understanding how photoexcitation affects reactivity. In this work, we address both of these issues. We present experimental data for a series of aromatically substituted pyrroles and indoles, and show that quantifying induced atomic forces upon photoexcitation provides a powerful predictive model for determining whether a given reactant will photoplanarise and hence proceed to photocyclised product under appropriate reaction conditions. The propensity of a molecule to photoplanarise is related to localised changes in charge distribution around the putative forming ring upon photoexcitation. This is promoted by asymmetry in molecular structures and/or charge distributions, inclusion of heteroatoms and ethylene bridging and well-separated or isolated photocyclisation sites.

Rhodium(iii)-catalyzed indole synthesis at room temperature using the transient oxidizing directing group strategy

Rh-catalyzed reactions of N-alkyl anilines with internal alkynes at room temperature have been developed using an in situ generated N-nitroso group as a transient oxidizing directing group. Due to mild reaction conditions, this method enabled synthesis of a broad range of N-alkyl indoles, including even two indole-based medicinal compounds. Our work disclosed the feasibility of the transient oxidizing directing group strategy in C-H functionalization reactions, which possesses the potential to enhance overall step-economy and impart new reactivity patterns to substrates.

Indole derivative and its preparation method (by machine translation)

The present invention provides indole derivative and its preparation method, comprises the following steps: a compound represented by formula I, additive and solvent mixed, in nitrogen or argon and visible light illumination under the conditions of reaction, to obtain the indole derivatives. In a nitrogen or argon atmosphere, through visible light radiation excitation I shown in the polyurea compound of carbon oxygen key, then the occurrence of [1, 6] - H migration, eventually through the intramolecular radical coupling and dehydration reaction for the synthesis of indole derivatives, the whole process needs no photocatalyst participation, the operation is simple, mild condition, high yield, accords with the atom economic and environmental protection, for the industrial preparation of indole derivatives having a high reference value. (by machine translation)

Rhodium-catalyzed annulation of tertiary aniline N-oxides to N-alkylindoles: Regioselective C-H activation, oxygen-atom transfer, and N-dealkylative cyclization

[Cp?RhIII]-catalyzed annulation of tertiary aniline N-oxides with alkynes was reported to achieve the challenging ortho C-H functionalization of tertiary anilines via N-O bond acting as a traceless directing group. More significantly, this system represents the first example which integrates C-H activation, oxygen-atom transfer, and N-dealkylative cyclization in one reaction. This unprecedented coupling reaction has allowed the construction of N-alkylindole derivatives in high efficiency with broad substrate scope and good functional group tolerance.

Rh(III)-catalyzed chemoselective C-H functionalizations of tertiary aniline: N -oxides with alkynes

In this work, we report novel Rh(iii)-catalyzed chemoselective functionalizations of tertiary aniline N-oxides with alkynes, including annulation via the sequential C(sp2)-H and C(sp3)-N activation for the formation of N-alkylindoles and an O-atom transfer (OAT) process for the synthesis of acetophenones.

Rhodium(III)-catalyzed synthesis of indoles from 1-alkylidene-2- arylhydrazines and alkynes via C-H and N-N bond cleavages

1-Alkylidene-2-arylhydrazines undergo annulative coupling with internal alkynes in the presence of a rhodium(III) catalyst and a copper(II) salt. The reaction proceeds through cleavage of the C-H and N-N bonds of hydrazines to afford 1,2,3-trisubstituted indole derivatives.

Palladium-catalyzed one-pot three- or four-component coupling of aryl iodides, alkynes, and amines through C-N bond cleavage: Efficient synthesis of indole derivatives

An efficient synthesis of N-substituted indole derivatives was realized by combining the Pd-catalyzed one-pot multicomponent coupling approach with cleavage of the C(sp3)-N bonds. Three or four components of aryl iodides, alkynes, and amines were involved in this coupling process. The cyclopentadiene-phosphine ligand showed high efficiency. A variety of aryl iodides, including cyclic and acyclic tertiary amino aryl iodides, and substituted 1-bromo-2-iodobenzene derivatives could be used. Both symmetric and unsymmetric alkynes substituted with alkyl, aryl, or trimethylsilyl groups could be applied. Cyclic secondary amines such as piperidine, morpholine, 4-methylpiperidine, 1-methylpiperazine, 2-methylpiperidine, and acyclic amines including secondary and primary amines all showed good reactivity. Further application of the resulting indole derivatives was demonstrated by the synthesis of benzosilolo[2,3-b]indole. All in one: Efficient synthesis of N-substituted indole derivatives was realized by combining a Pd-catalyzed one-pot multicomponent coupling approach with the cleavage of C(sp 3)-N bonds (see scheme). Three or four components of aryl iodides, alkynes, and amines were involved in this coupling process. The cyclopentadiene-phosphine ligand (1) showed high efficiency. Copyright

Traceless directing strategy: Efficient synthesis of N-alkyl indoles via redox-neutral C-H activation

A general protocol for the synthesis of N-alkyl indoles has been developed via a redox neutral C-H activation strategy using a traceless nitroso directing group. A broad scope of substituted N-alkyl indoles has been prepared in good to excellent yields using a very simple Rh catalyst system in the absence of an external oxidant or any other additive. Good to excellent regioselectivity has been achieved for asymmetrically disubstituted acetylenes.