121194-51-2

Upstream product

• 82490-61-7 3-phenyl-2-propyn-1-yl methanesulfonate 
• 62-53-3 aniline 
• 614-45-9 tert-Butyl peroxybenzoate 
• 536-74-3 phenylacetylene 
• 100-61-8 N-methylaniline 
• 80-43-3 bis(1-methyl-1-phenylethyl)peroxide 
• 75-91-2 tert.-butylhydroperoxide 
• 2579-22-8 Phenylpropargyl aldehyde 
• 50-00-0 formaldehyd 
• 3355-31-5 1-chloro-3-phenyl-2-propyne 
• 100-62-9 N-methylenebenzenamine 
• 34706-60-0 N-methyl-3-phenylprop-2-yn-1-amine 
• 14465-74-8 N-phenyl-N-prop-2-ynylamine 
• 591-50-4 iodobenzene 

Downstream Products

• 203064-65-7 (Dimethyl-vinyl-silanyl)-phenyl-(3-phenyl-prop-2-ynyl)-amine 
• 3445-76-9 5-phenyl-3H-1,2-dithiole-3-thione 
• 605-03-8 4-phenylquinoline 
• 30290-78-9 4-phenyl-1,2,3,4-tetrahydroquinoline 

Relevant academic research and scientific papers

Propargylamine synthesis via sequential methylation and C–H functionalization of N-methylanilines and terminal alkynes under metal–organic framework Cu2(BDC)2(DABCO) catalysis

A crystalline porous metal–organic framework Cu2(BDC)2(DABCO) was synthesized and characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR), atomic absorption spectrophotometry (AAS), hydrogen temperature-programmed reduction (H2-TPR), and nitrogen physisorption measurements. The Cu2(BDC)2(DABCO) was used as a heterogeneous catalyst for the direct C–C coupling reaction via cascade methylation and C–H functionalization of N-methylaniline and terminal alkynes. tert-Butyl hydroperoxide also served as the methylating reagent in the transformation, and N-methyl-N-(3-phenylprop-2-ynyl)benzenamine but not N-(3-phenylprop-2-ynyl)benzenamine was produced as the principal product. The Cu-MOF could be recovered and reused several times without a significant degradation in catalytic activity. To the best of our knowledge, the direct oxidative C–C coupling between N-methylaniline and alkynes with methylation transformation was not previously mentioned in the literature.

Direct and selective N-monoalkynylation and N-monoalkenylation of anilines with alky(e)nyl methanesulfonates using methylmagnesium bromide as a base

Several anilines were directly N-monoalkynylated and N-monoalkenylated with alkynyl methanesulfonates and alkenyl methanesulfonates, respectively, using methylmagnesium bromide as a base in good yields with high selectivities.

Efficient and robust superparamagnetic copper ferrite nanoparticle-catalyzed sequential methylation and C-H activation: Aldehyde-free propargylamine synthesis

We have described a method for oxidative cross-coupling reactions between N-alkyl anilines and terminal alkynes forming N-aryl-N-methylpropargylamines. Superparamagnetic CuFe2O4 nanoparticles were employed as efficient and robust catalyst. The optimum conditions involved the use of tert-butyl hydroperoxide (TBHP) as oxidant and methylating reagent in dimethylacetamide (DMA) solvent at 140 °C. The two-step reaction, methylation and C-C cross-coupling, proceeds efficiently and has high selectivity, and good conversions were achieved in short reaction times. Preliminary mechanistic investigation was conducted. The CuFe2O4 nanoparticles could be facilely separated from the reaction mixture by magnetic decantation and could be reused several times with only a slight decrease in catalytic activity.

Ag-Catalyzed or Ag/PPh3-Catalyzed Chemoselective Switchable Cascade Reactions of N-Propargyl Thiocarbamoyl Fluorides and Malonate Esters

The divergent chemoselective synthesis of 2-methylene-2,3-dihydrothiazoles and 4-benzylidene pyrrolidine-2-thiones (most with E stereoselectivity) from N-propargyl thiocarbamoyl fluorides and malonate esters in moderate to excellent yields with a broad substrate scope and functional group tolerance has been accomplished. AgNTf2 catalyst at 60 °C in dichloroethane provided 4-benzylidene pyrrolidine-2-thiones. AgOTf catalyst and PPh3 ligand in refluxing acetonitrile resulted in a complete switch in the reactivity of formed α,α-diester thioamide intermediates followed by isomerization to access 2-methylene-2,3-dihydrothiazoles.

BF3·Et2O as a metal-free catalyst for direct reductive amination of aldehydes with amines using formic acid as a reductant

A versatile metal- and base-free direct reductive amination of aldehydes with amines using formic acid as a reductant under the catalysis of inexpensive BF3·Et2O has been developed. A wide range of primary and secondary amines and diversely substituted aldehydes are compatible with this transformation, allowing facile access to various secondary and tertiary amines in high yields with wide functional group tolerance. Moreover, the method is convenient for the late-stage functionalization of bioactive compounds and preparation of commercialized drug molecules and biologically relevant N-heterocycles. The procedure has the advantages of simple operation and workup and easy scale-up, and does not require dry conditions, an inert atmosphere or a water scavenger. Mechanistic studies reveal the involvement of imine activation by BF3and hydride transfer from formic acid.

Copper-Catalyzed Tandem Sulfuration/Annulation of Propargylamines with Sulfur via C-N Bond Cleavage

Copper-catalyzed aerobic oxidative sulfuration and annulation of propargylamines with elemental sulfur is described. The tandem reaction involves C-N bond cleavage and the formation of multiple C-S bonds, affording 1,2-dithiole-3-thiones in good to excellent yields with good functional group tolerance.

Hypervalent iodine compound containing heterocyclic ring as well as preparation method and application thereof

The invention discloses a hypervalent iodine compound containing a heterocyclic ring as well as a preparation method and application thereof. A structure of the compound is shown as a formula (I): theformula (I) is shown in the description, wherein R is selected from hydrogen, halogen, alkyl, alkoxy, halogenated alkyl, halogenated alkoxy, nitryl, cyano, hydroxyl or -COOR'; R' is alkyl or halogenated alkyl; and Het is substituted or non-substituted 1,4-benzopyranone, substituted or non-substituted quinolone, substituted or non-substituted isoquinoline, substituted or non-substituted thiobenzopyranone, substituted or non-substituted coumarin and substituted or non-substituted oxepin. The compound disclosed by the invention is novel in structure and is the hypervalent iodine compound containing the heterocyclic ring; the hypervalent iodine compound is stable in structure and simple in preparation method; and meanwhile, the hypervalent iodine compound has a very good inhibition effect onML-1 and MOLM-13 cells and has an extremely great application prospect on prevention and/or treatment effect on leukemia.

Heterocyclic Iodoniums for the Assembly of Oxygen-Bridged Polycyclic Heteroarenes with Water as the Oxygen Source

A diverse set of novel heterocyclic iodoniums was synthesized for the first time. The reactions of these unique iodoniums with environmentally benign water as the oxygen source provided structurally complex oxygen-incorporated heteropolycycles that are essential motifs in natural products and biologically active compounds. The transformation only required low-cost copper acetate. Further derivatization of the obtained polycycles expanded the structural diversity, which is important in the building of chemical libraries for drug discovery.

Mechanistic Insights into the B(C6F5)3-Initiated Aldehyde-Aniline-Alkyne Reaction to Form Substituted Quinolines

A substoichiometric quantity of the Lewis acid B(C6F5)3 is sufficient to initiate the aldehyde-amine-alkyne reaction, in a one-pot methodology that enables the synthesis of a range of functionalized quinolines. Optimization studies revealed that key requirements for the high-yielding tricomponent reaction initiated by B(C6F5)3 at raised temperatures include an excess of the in situ generated imine (which acts as a hydrogen acceptor) and an alkyne substituent able to stabilize positive charge buildup during the cyclization. Mechanistic experiments revealed that under these conditions B(C6F5)3 is acting as a Lewis acid-assisted Br?nsted acid, with H2O-B(C6F5)3 being the key species enabling catalytic quinoline formation. This was indicated by deuterium labeling studies and the observation that the cyclization of N-(3-phenylpropargyl)aniline using B(C6F5)3 under anhydrous conditions afforded the zwitterion [(N-H-3-B(C6F5)3-4-Ph-quinolinium], which does not undergo protodeboronation to release B(C6F5)3 and the quinoline product under a range of conditions. Finally, a brief substrate scope exploration demonstrated that this is an operationally simple and effective methodology for the production of functionalized quinolines.

AgNO2 as the NO Source for the Synthesis of Substituted Pyrazole N-Oxides from N-Propargylamines

A straightforward method for synthesizing the pyrazole N-oxides from N-propargylamines and AgNO2 through oxidation/cyclization reaction had been developed. AgNO2 was used as the NO source for the first time to synthesize pyrazole N-o