95694-54-5

Upstream product

• 95-51-2 o-chloroaniline 
• 111-46-6 diethylene glycol 
• 110-91-8 morpholine 
• 147641-13-2 2-chlorophenyl nonaflate 
• 95-57-8 2-monochlorophenol 
• 694-80-4 2-bromo-1-chlorobenzene 
• 348-51-6 1-chloro-2-fluorobenzene 
• 34604-52-9 diethylene glycol dimesylate 
• 95-50-1 1,2-dichloro-benzene 
• 85070-48-0 2-fluoro-3-chlorobenzaldehyde 
• 1446818-89-8 3-chloro-2-(morpholin-4-yl)benzaldehyde 
• 88284-48-4 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 
• 23328-69-0 4-chloromorpholine 

Downstream Products

• 1444746-09-1 4-(4'-methoxy-[1,1'-biphenyl]-2-yl)morpholine 
• 1152887-64-3 N-benzyl-2-morpholinoaniline 
• 28276-88-2 2-(N-(2-chlorophenyl)formamido)ethyl formate 

Relevant academic research and scientific papers

N-heterocyclic carbene-Pd(II)-2-methyl-4,5-dihydrooxazole complex-catalyzed highly chemoselective mono-amination of dichlorobenzenes

The palladium-catalyzed chemoselective mono-amination of dichlorobenzenes was reported in this paper. Under the suitable conditions, all reactions involving the three isomers of dichlorobenzenes with various secondary and primary amines in the presence of

Catalyst-free photodecarbonylation ofortho-amino benzaldehyde

It is almost a consensus that decarbonylation of the aldehyde group (-CHO) needs to not only be mediated by transition metal catalysts, but also requires severe reaction conditions (high temperature and long reaction time). In this work, inspired by the “conformational-selectivity-based” design strategy, we broke this consensus and discovered a catalyst-free photodecarbonylation of the aldehyde group. It revealed that decarbonylation can be easily achieved with visible light irradiation by introducing a tertiary amine into theortho-position of the aldehyde group. A diverse array of tertiary amines is tolerated by our photodecarbonylation under mild conditions. Furthermore, the (QM) computations of the mechanism and the experiments on well-designed special substrates revealed that our photodecarbonylation depends on the conformational specificity of the aldehyde group and tertiary amine, and occurs through an unusual [1,4]-H shift and a subsequent [1,3]-H shift.

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.

Transition-Metal-Catalyzed Amination of Aryl Fluorides

Arene activation via transition-metal (TM) η 6-coordination has merged as a powerful method to diversify the aromatic C-F bond, which is relatively less reactive due to its high bond energy. However, this strategy in general requires to use largely excess arenes or TM η 6-complexes as the substrates. Herein, we highlight our recent work on the catalytic S NAr amination of electron-rich and electron-neutral aryl fluorides that are inert in classical S NAr reactions. This protocol enabled by a Ru/hemilabile ligand catalyst covers a broad scope of substrates without wasting arenes. Mechanistic studies revealed that the nucleo?-philic substitution proceeded on a Ru η 6-arene complex, and the hemilabile ligand significant promoted the arene dissociation.

Practical Catalytic Cleavage of C(sp3)?C(sp3) Bonds in Amines

The selective cleavage of thermodynamically stable C(sp3)?C(sp3) single bonds is rare compared to their ubiquitous formation. Herein, we describe a general methodology for such transformations using homogeneous copper-based catalysts in the presence of air. The utility of this novel methodology is demonstrated for Cα?Cβ bond scission in >70 amines with excellent functional group tolerance. This transformation establishes tertiary amines as a general synthon for amides and provides valuable possibilities for their scalable functionalization in, for example, natural products and bioactive molecules.

Mechanism and Scope of Base-Controlled Catalyst-Free N-Arylation of Amines with Unactivated Fluorobenzenes

A general method for transition metal-free N-arylation of amines has been developed. Mechanistic studies have revealed that the ability of the base to facilitate the desired amination without promoting unwanted side reactions is the guiding factor. By employing lithium bis(trimethylsilyl)amide as a base the resultant deprotonated amines readily react with a range of unactivated fluorobenzene derivatives. This new arylation method is utilized for the simple two-step synthesis of the antidepressant Vortioxetine.

ARYLATION OF ALIPHATIC AMINES

The invention relates to a method for arylation of amines, such as aliphatic amines by reaction of aryl-halogens, e.g. chloro- or fluorobenzene derivatives without strongly electron withdrawing substituents in the presence of a strong base.

Mechanistic Insight Leads to a Ligand Which Facilitates the Palladium-Catalyzed Formation of 2-(Hetero)Arylaminooxazoles and 4-(Hetero)Arylaminothiazoles

By using mechanistic insight, a new ligand (EPhos) for the palladium-catalyzed C?N cross-coupling between primary amines and aryl halides has been developed. Employing an isopropoxy group at the C3-position favors the C-bound isomer of the ligand-supported palladium(II) complexes and leads to significantly improved reactivity. The use of a catalyst system based on EPhos with NaOPh as a mild homogeneous base proved to be very effective in the formation of 4-arylaminothiazoles and highly functionalized 2-arylaminooxazoles. Previously, these were not readily accessible using palladium catalysis.

Synthesis of ortho -haloaminoarenes by aryne insertion of nitrogen-halide Bonds

A rapid and general access to ortho-haloaminoarenes has been developed by aryne insertion into N-chloramine, N-bromoamine, and N-iodoamine bonds via two complementary protocols harnessing fluoride-promoted 1,2-elimination of ortho-trimethylsilyl aryltriflates. Typically, electron-deficient N-chloramines effectively react with aryne intermediates generated at elevated temperature with CsF, while less stable N-haloamines are found more efficient under milder, TBAF-mediated aryne formation at room temperature. Both protocols demonstrate a good level of regioselectivity and functional group tolerance. Efforts to elucidate the mechanism of N-X insertion are also discussed. The practical value of this transformation is highlighted by rapid synthesis of novel analogues of the antipsychotic cariprazine.

Rapid and convenient synthesis of N-arylmorpholines under microwave irradiation

A series of N-arylmorpholines 1a-1n was obtained by cyclocondensation of arylamines and diethylene glycol dimesylate under microwave irradiation in an aqueous potassium carbonate medium. The reaction is rapid and convenient, and a variety of functional groups are tolerated in the process.