169963-54-6

Upstream product

• 110-91-8 morpholine 
• 92-66-0 4-bromo-1,1'-biphenyl 
• 613-37-6 4-methoxylbiphenyl 
• 28355-52-4 2-([1,1′-biphenyl]-4-yloxy)pyridine 
• 10389-51-2 1-morpholino-4-nitrobenzene 
• 98-80-6 phenylboronic acid 
• 19813-76-4 4-phenylthioanisole 
• 2524-67-6 4-morpholino-4-yl-phenylamine 
• 100-58-3 phenylmagnesium bromide 
• 549512-93-8 [1,1'-biphenyl]-4-yl morpholine-4-carboxylate 
• 92-69-3 4-Phenylphenol 
• 17763-78-9 4-phenylphenyl triflate 
• 188114-77-4 [1,1'-biphenyl]-4-yl pivalate 
• 3933-94-6 4-Phenoxybiphenyl 

Downstream Products

• 5123-05-7 2-([1,1'-biphenyl]-4-yl)-5,5-dimethyl-1,3,2-dioxaborinane 

Relevant academic research and scientific papers

Morpholine derivative oxidation ring-opening method and product thereof

The invention relates to a morpholine derivative oxidation ring-opening method and a product thereof, and belongs to the technical field of compound preparation. The method for promoting oxidative cracking of C (sp3)-C (sp3) bonds of a morpholine derivative by visible light has been successfully developed under the inspiration of the design concept of visible light induced C (sp3)-C (sp3) bond cracking. According to the morpholine derivative oxidation ring-opening method, C (sp3)-C (sp3) bonds without ring stress are cracked by using visible light as an energy source and O2 as a final oxidizing agent, use of transition metal, high temperature, high pressure and chemical equivalent dangerous oxidizing agents is avoided, good functional group tolerance is established, 30 substrates are obtained, the yield is as high as 83%, and a supplementary scheme is provided for realizing oxidative cracking of the morpholine derivative under a mild condition.

Visible-Light-Mediated Aerobic Oxidative C(sp3)?C(sp3) Bond Cleavage of Morpholine Derivatives Using 4CzIPN as a Photocatalyst

Herein, a metal-free strategy for the aerobic oxidative cleavage of the inert C(sp3)?C(sp3) bond was developed. Deconstruction of morpholine derivatives was conducted using visible light as an energy source and O2 as an oxidant under mild conditions. This procedure demonstrated suitable selectivity and functional group tolerance. Moreover, a possible mechanism involving a radical process was proposed based on a series of mechanism exploration and control experiments. (Figure presented.).

NHC-Nickel Catalyzed C-N Bond Cleavage of Mono-protected Anilines for C-C Cross-Coupling

A Ni-catalyzed aryl C-N bond cleavage of mono-protected anilines, N-arylsulfonamides, has been developed. A new N-heterocyclic carbene derived from benzoimidazole shows high reactivity for the C-N cleavage/C-C cross-coupling reaction. The ortho-directing group is not required to break the C-N bond of sulfonyl-protected anilines, which are not limited to π-extended anilines. The mechanistic studies have revealed that a sulfamidomagnesium salt is the key coupling intermediate.

Nickel-Catalyzed Amination of Aryl Thioethers: A Combined Synthetic and Mechanistic Study

Herein, we report a nickel-1,2-bis(dicyclohexylphosphino)ethane (dcype) complex for the catalytic Buchwald-Hartwig amination of aryl thioethers. The protocol shows broad applicability with a variety of different functional groups tolerated under the catalytic conditions. Extensive organometallic and kinetic studies support a nickel(0)-nickel(II) pathway for this transformation and revealed the oxidative addition complex as the resting state of the catalytic cycle. All the isolated intermediates have proven to be catalytically and kinetically competent catalysts for this transformation. The fleeting transmetalation intermediate has been successfully synthesized through an alternative synthetic organometallic pathway at lower temperature, allowing for in situ NMR study of the C-N bond reductive elimination step. This study addresses key factors governing the mechanism of the nickel-catalyzed Buchwald-Hartwig amination process, thus improving the understanding of this important class of reactions.

Immobilized Pd on a NHC functionalized metal–organic framework MIL-101(Cr): an efficient heterogeneous catalyst in Suzuki?Miyaura coupling reaction in water

A novel Pd?NHC functionalized metal–organic framework (MOF) based on MIL-101(Cr) was synthesized and used as an efficient heterogeneous catalyst in the C-C bond formation reactions. Using this heterogeneous Pd catalyst system, the Suzuki?Miyaura coupling reaction was accomplished well in water, and coupling products were obtained in good to excellent yields in short reaction time. The Pd?NHC?MIL-101(Cr) was characterized using some different techniques, including Fourier transform-infrared, X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy, inductively coupled plasma and elemental analysis. The microscopic techniques showed the discrete octahedron structure of MIL-101(Cr), which is also stable after chemical modification process to prepare the catalyst system. The TEM images of the catalyst showed the existence of palladium nanoparticles immobilized in the structure of the catalyst, while no reducing agent was used. It seems that the NHC groups and imidazolium moieties in the structure of the MOF can reduce Pd (II) to Pd (0) species. This modified MOF substrate can also prevent aggregation of Pd nanoparticles, resulting in high stability of them in organic transformation. The Pd?NHC?MIL-101(Cr) catalyst system could be simply extracted from the reaction mixture, providing an efficient synthetic method for the synthesis of biaryls derivatives using the aforementioned coupling reaction. The Pd?NHC?MIL-101(Cr) catalyst could be recycled in this organic reaction with almost consistent catalytic efficiency.

Ru(II)-Catalyzed Amination of Aryl Fluorides via η6-Coordination

We developed a Ru/hemilabile-ligand-catalyzed nucleophilic aromatic substitution (SNAr) of aryl fluorides as the limiting reagents. Significant ligand enhancement was demonstrated by the engagement of both electron-rich and neutral arenes in the SNAr amination without using excess arenes. Preliminary mechanistic studies revealed that the nucleophilic substitution proceeds on a η6-complex of the Ru catalyst and the substrate, and the hemilabile ligand facilitates dissociation of products from the metal center.

Sterically hindered N-heterocyclic carbene/palladium(ii) catalyzed Suzuki-Miyaura coupling of nitrobenzenes

Palladium-catalyzed denitrative Suzuki coupling of nitroarenes using 2-aryl-5-(2,4,6-triisopropylphenyl)-2,3-imidazolylidene[1,5-a]pyridines as the ligands is described. The key to success is the use of the NHC ligands which show strong donating ability and suitable steric hindrance allowing the successful oxidative addition of Ar-NO2 bonds. Both aromatic and aliphatic boronic acids are tolerated, and a variety of biphenyls and alkylarenes were obtained in good to excellent yields.

Method for synthesizing aromatic compound by coupling palladium/imidazole salt with nitroaromatic hydrocarbon and boric acid compound (by machine translation)

The invention discloses a method, for coupling a palladium/imidazole salt with a nitroaromatic hydrocarbon and a boric acid compound to synthesize an aromatic compound. The method comprises: in organic solvent, taking nitroaromatic hydrocarbon and boric acid compound as substrate, palladium/imidazole salt as a catalyst, carrying out coupling reaction under the action of alkali, and carrying out post-treatment to obtain the aromatic compound. The method is simple, easy to store, low in price, relatively low in ligand consumption, high in product yield, good in substrate applicability, and suitable for alkyl boronic acid. The process of the invention can be used to synthesize a series of aromatic compounds, for example. The compound has wide application value in the fields of pesticides, medicines, materials and the like. (by machine translation)

Nickel-Catalyzed Decarboxylation of Aryl Carbamates for Converting Phenols into Aromatic Amines

Herein, we describe a new catalytic approach to accessing aromatic amines from an abundant feedstock, namely phenols. The most reliable catalytic method for converting phenols to aromatic amines uses an activating group, such as a trifluoromethane sulfonyl group. However, this activating group is eliminated as a leaving group during the amination process, resulting in significant waste. Our nickel-catalyzed decarboxylation reaction of aryl carbamates forms aromatic amines with carbon dioxide as the only byproduct. As this amination proceeds in the absence of free amines, a range of functionalities, including a formyl group, are compatible. A bisphosphine ligand immobilized on a polystyrene support (PS-DPPBz) is key to the success of this reaction, generating a catalytic species that is significantly more active than simple nonsupported variants.

[Pd(IPr*R)(acac)Cl]: Efficient bulky Pd-NHC catalyst for Buchwald-Hartwig C-N cross-coupling reaction

A series of bulky palladium catalysts based on N-heterocyclic carbene, (Pd(NHC)(acac)Cl: NHC = IPr*me = N,N′-bis(2,6-bis(di-p-tolylmethyl)-4-methylphenyl)-imidazol-2 -ylidene, Pd(IPr*me)(acac)Cl; NHC = IPr*ipr = N,N′-bis(2,6-bis(di-4-isopropylphenyl)-4-methylphenyl)-imidazol-2 -ylidene, Pd(IPr*ipr)(acac)Cl; and NHC = IPr*tBu = N,N′-bis(2,6-bis(di-4-(tert-butyl)phenyl)- 4-methylphenyl)- imidazol-2-ylidene, Pd(IPr*tBu)(acac)Cl; acac = acetylacetonate), have been designed and synthesized. These three new catalysts showed much better catalytic activity in the Buchwald?Hartwig arylamination coupling reaction as compare to the earlier congener (IPr*)Pd(acac)Cl (IPr* = N,N′-bis(2,6-diphenylmethyl)-4-methylphenylimidazol-2-ylidene). The highly active PdII precatalyst [Pd(IPr*me)(acac)Cl] has been fully explored by using a wide range of substrates with different electronic and steric demands of coupling partners, for which up to 99% isolated yields were obtained. Remarkably, the moderate isolated yield was obtained for the challenging coupling of the amine bearing very bulky groups.