4096-20-2

Usage

Synthesis Reference(s)

Synthesis, p. 447, 1991 DOI: 10.1055/s-1991-26489

InChI:InChI=1/C11H15N/c1-3-7-11(8-4-1)12-9-5-2-6-10-12/h1,3-4,7-8H,2,5-6,9-10H2

Upstream product

• 142-68-7 TETRAHYDROPYRANE 
• 62-53-3 aniline 
• 110-89-4 piperidine 
• 462-06-6 fluorobenzene 
• 60-29-7 diethyl ether 
• 4442-11-9 lithium piperidide 
• 108-86-1 bromobenzene 
• 101-84-8 diphenylether 
• 127-63-9 diphenyl sulphone 
• 108-95-2 phenol 
• 110-00-9 furan 
• 108-90-7 chlorobenzene 
• 4789-09-7 1-phenylpiperidin-2-one 
• 5768-13-8 N-phenylglutarimide 

Downstream Products

• 677764-87-3 (4-(piperidin-1-yl)phenyl)methanol 
• 53926-62-8 bis(4-(piperidin-1-yl)phenyl)methane 
• 412343-59-0 (5-bromo-pentyl)-phenyl-carbamonitrile 
• 109019-39-8 1-methyl-1-phenylpiperidinium iodide 
• 22148-20-5 N-(4-bromophenyl)piperidine 
• 2359-60-6 4-(1-piperidino)aniline 
• 52695-16-6 1-(4-nitroso-phenyl)-piperidine 
• 6574-15-8 1-(4-nitrophenyl)piperidine 
• 839-93-0 1-(2,4-dinitrophenyl)piperidine 
• 89505-35-1 5-Nitro-2-(4-piperidin-1-yl-phenylazo)-benzonitrile 
• 89505-30-6 (4-Piperidin-1-yl-phenyl)-(4-trifluoromethyl-phenyl)-diazene 
• 40904-88-9 (4-Piperidin-1-yl-phenyl)-p-tolyl-diazene 
• 89505-28-2 (4-Chloro-phenyl)-(4-piperidin-1-yl-phenyl)-diazene 
• 89505-31-7 1-[4-(4-Piperidin-1-yl-phenylazo)-phenyl]-ethanone 

Relevant academic research and scientific papers

Palladium-catalyzed synthesis of arylamines from diphenyliodonium tetrafluoroborate and secondary amine

The hetero-cross coupling reaction of diphenyliodonium tetrafluoroborate with secondary amine in the presence of LiNTMS2 or NaOtBu as base, Pd2(dba)3?CHCl3 as catalyst, and tri-o-tolylphosphine as ligand afforded arylamines at room temperature under mild conditions.

Phosphines with N-Heterocyclic Boryl-Substituents: Ligands for Coordination Chemistry and Catalysis

Boryl-substituted phosphines NHB–P(R)Ph (R = H, Ph, NHB = N-heterocyclic boryl substituent) react with Fe2(CO)9 to give isolable Fe(CO)4 complexes, two of which were characterized by single-crystal XRD studies. The electronic and steric properties for a series of the boryl phosphines were further assessed by evaluation of TEPs for in-situ formed complexes [RhCl(NHB–PR1R2)(CO)2] (R1, R2 = H, Ph, Me, NMe2), and calculations of buried volumes for Fe(CO)4 complexes. The results imply that the NHB-phosphines exhibit due to their conformational flexibility some variability in their steric bulk, and that some specimens may exhibit similar electron releasing power and steric demand as tBu3P. Studies of the amination of bromobenzene with 2,6-diisopropylaniline confirmed that these properties can be exploited to promote Pd-catalyzed C–N cross coupling reactions, and that formal replacement of a phenyl by a NHB substituent in the auxiliary phosphine has a beneficial effect on catalyst performance.

Synthesis, characterisation and reactivity of copper(I) amide complexes and studies on their role in the modified Ullmann amination reaction

A series of copper(I) alkylamide complexes have been synthesised; copper(I) dicyclohexylamide (1), copper(I) 2,2,6,6-tetramethylpiperidide (2), copper(I) pyrrolidide (3), copper(I) piperidide (4), and copper(I) benzylamide (5). Their solid-state structures and structures in [D6]benzene solution are characterised, with the aggregation state in solution determined by a combination of DOSY NMR spectroscopy and DFT calculations. Complexes 1, 2 and 4 are shown to exist as tetramers in the solid state by X-ray crystallography. In [D6]benzene solution, complexes 1, 2 and 5 were found by using 1H DOSY NMR to exist in rapid equilibrium between aggregates with average aggregation numbers of 2.5, 2.4 and 3.3, respectively, at 0.05 M concentration. Conversely, distinct trimeric, tetrameric and pentameric forms of 3 and 4 were distinguishable by one-dimensional 1H and 1H DOSY NMR spectroscopy. Complexes 3-5 are found to react stoichiometrically with iodobenzene, in the presence or absence of 1,10-phenanthroline as an ancillary ligand, to give arylamine products indicative of their role as potential intermediates in the modified Ullmann reaction. The role of phenanthroline has also been explored both in the stoichiometric reaction and in the catalytic Ullmann protocol.

Synthesis of N-heterocyclic carbene-Pd(II)-5-phenyloxazole complexes and initial studies of their catalytic activity toward the Buchwald-Hartwig amination of aryl chlorides

Three new N-heterocyclic carbene (NHC)-Pd(II) complexes using 5-phenyloxazole as the ancillary ligand have been obtained in moderate to good yields by a one-pot reaction of the corresponding imidazolium salts, palladium chloride and 5-phenyloxazole under mild conditions. Initial studies showed that one of the complexes is an efficient catalyst for the Buchwald-Hartwig amination of aryl chlorides with various secondary and primary amines under the varied catalyst loading of 0.01-0.05 mol%, thus it will enrich the chemistry of NHCs and give an alternative catalyst for the coupling of challenging while cost-low aryl chlorides.

Iridium and bis(4-nitrophenyl)phosphoric acid catalysed amination of diol by hydrogen-borrowing methodology for the synthesis of cyclic amine: Synthesis of clopidogrel

The borrowing hydrogen method is an environmentally benign process for the synthesis of amines, as H2O is the side product. A new green process for the amination of diol by [Ir] catalyst 15 and bis(4-nitrophenyl)phosphoric acid for the synthesis of cyclic amine is reported. This method was successfully applied for the synthesis of antiplatelet drug clopidogrel.

Iodine-Mediated Coupling of Cyclic Amines with Sulfonyl Hydrazides: an Efficient Synthesis of Vinyl Sulfone Derivatives

An efficient iodine-mediated coupling of cyclic amines with sulfonyl hydrazides is reported. This transformation opens a new route to the synthesis of vinyl sulfones derivatives, which is a common structural motif in natural products and pharmaceuticals. Tentative mechanistic studies suggest that this reaction is likely to involve a radical process.

Organic photoredox catalytic α-C(sp3)-H phosphorylation of saturated: Aza -heterocycles

A metal-free C(sp3)-H phosphorylation of saturated aza-heterocycles via the merger of organic photoredox and Br?nsted acid catalyses was established under mild conditions. This protocol provided straightforward and economic access to a variety of valuable α-phosphoryl cyclic amines by using commercially available diarylphosphine oxide reagents. In addition, the D-A fluorescent molecule DCQ was used for the first time as a photocatalyst and exhibited an excellent photoredox catalytic efficiency in this transformation. A series of mechanistic experiments and DFT calculations demonstrated that this transformation underwent a sequential visible light photoredox catalytic oxidation/nucleophilic addition process.

Nickel-Catalyzed Amination of Aryl Chlorides with Amides

A nickel-catalyzed amination of aryl chlorides with diverse amides via C-N bond cleavage has been realized under mild conditions. A broad substrate scope with excellent functional group tolerance at a low catalyst loading makes the protocol powerful for synthesizing various aromatic amines. The aryl chlorides could selectively couple to the amino fragments rather than the carbonyl moieties of amides. Our protocol complements the conventional amination of aryl chlorides and expands the usage of inactive amides.

Synthesis method of 1-(4-bromophenyl) piperidine

The invention discloses a preparation method of 1-(4-bromophenyl) piperidine, and belongs to the technical field of medical intermediates. Bromobenzene and piperidine are used as raw materials and react with potassium tert-butoxide or sodium tert-amyl alcohol in sulfolane in a heating mode to obtain N-phenyl piperidine; and then in the presence of a catalyst tetra-n-butyl tetraphenyl ammonium borate, a bromination reagent is added to react to obtain the 1-(4-bromophenyl)piperidine. The method is few in reaction steps, simple and convenient to operate and relatively high in yield, and a new path is provided for synthesis of the 1-(4-bromophenyl) piperidine.

Highly Chemoselective Deoxygenation of N-Heterocyclic N-Oxides Using Hantzsch Esters as Mild Reducing Agents

Herein, we disclose a highly chemoselective room-temperature deoxygenation method applicable to various functionalized N-heterocyclic N-oxides via visible light-mediated metallaphotoredox catalysis using Hantzsch esters as the sole stoichiometric reductant. Despite the feasibility of catalyst-free conditions, most of these deoxygenations can be completed within a few minutes using only a tiny amount of a catalyst. This technology also allows for multigram-scale reactions even with an extremely low catalyst loading of 0.01 mol %. The scope of this scalable and operationally convenient protocol encompasses a wide range of functional groups, such as amides, carbamates, esters, ketones, nitrile groups, nitro groups, and halogens, which provide access to the corresponding deoxygenated N-heterocycles in good to excellent yields (an average of an 86.8% yield for a total of 45 examples).