A sulfonate-based Cu(Ⅰ) metal-organic framework as a highly efficient and reusable catalyst for the synthesis of propargylamines under solvent-free conditions

A new highly efficient and reusable Cu（I）-MOF has been developed for the synthesis of propargylamine compounds via the three-component reaction of secondary amines, alkynes, and aromatic aldehydes under solvent-free conditions. The desired propargylamines were obtained in good to excellent yields with a low catalyst loading. The catalyst may be recovered and reused for up to 5 cycles without major loss of activity. This protocol has the advantages of excellent yields, low catalyst loading, and catalyst recyclability.

Facile synthesis of α-difluoromethyl α-propargylamines from CF_2H-substituted N-tert-butanesulfinyl ketimines

Stereoselective approach for preparation ofα-difluoromethylα-propargylamines has been developed.1,2-Addition of lithium acetylides to diverse chiral difluoromethylated（S）-N-tert-butanesulfinyl ketimines by using Ti（O^iPr）_4 as catalyst and THF as solvent afforded N-tert-butanesulfinamides in good to excellent yields（51-93%） and good diastereoselectivities（dr.85：15 to 93：7）.The N-tert -butanesulfinyl group can be readily cleaved under mild acidic condition（4 mol/L HCl in dioxane） to provide the correspondingα-difiuoromethylα-propargylamine in excellent yields（90-95%）.

Cu(II)salen配合物催化三组分偶联反应合成炔丙胺(英文)

A one pot three‐component coupling reaction of phenylacetylene, aldehyde, and amine derivatives in the presence of Cu(II) Salen complex as an efficient heterogeneous catalyst under solvent‐free conditions is reported. The catalyst displayed high activity and afforded the corresponding propargylamines in good to excellent yields. This method provides a wide range of substrate applicability. The catalyst was reused several times without significant loss of its catalytic activity.

Synthesis,Crystal Structure and Fluorescence of a Bicyclic Product Containing Chromene and Propargylamine Skeleton

The bicyclic product containing a chromene skeleton and a propargylamine skeleton（C（22）H（22）N2O2） was synthesized from the double sites of terminal alkyne, piperazine derivative and formaldehyde via one-pot procedure. Its structure was characterized by ^1H NMR, ^13C NMR, IR and H RMS, and further confirmed by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 12.6571（14）, b = 11.3249（12）, c = 12.6571（14） A, β = 105.22°,V = 1750.6（3） A^3, Z = 4, R = 0.0568 and w R = 0.1444. The fluorescence of the product was discussed.

Construction of a Self-assembling Intertwined Spiral Solvent Channel Based on Interactions between Macrocycles and CH_2Cl_2

The construction of an unprecedented intertwined spiral solvent channel is driven by weak C–Cl…O and C–H…N interactions based on extraordinary parallel spirals which were structured from supramolecular synthon macrocycle 1（C44H44N4O4） with a propargylamine backbone. The product is characterized by ^1H NMR, ^13C NMR, IR and HRMS, and further confirmed by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group C2/c, with a = 28.922（3）, b = 8.5069（9）, c = 21.687（2）A^°, β = 130.6320（10）°, V = 4049.4（7） A^°3 and Z = 8. A total of 11874 reflections were collected, of which 4942 were independent（Rint = 0.0590） and 2937 were observed with I 〉 2σ（I）. The final full-matrix least-squares refinement gave R（I 〉 2s（I）） = 0.069 and w R = 0.167, S = 1.05,（Δρ）max = 0.20 and（Δρ）min =-0.22 e·A^1-3. The fluorescence of the product is discussed.

Sequence [2,3]-Sigmatropic Rearrangement: One-Pot Synthesis of Proparggyl Allenylamines

Allenes,served as highly sought-after building blocks,are an indispensable component of synthetic chemistry.Their utility in modulating the chemical,physical,and pharmaceutical properties of organic compounds make allenes a desirable choice in various applications.Here,we report a facile method for the atom-economical synthesis of propargyl allenylamines via an underdeveloped[2,3]-sigmatropic rearrangement.Our strategy employs easily accessible propargylamines as starting materials,which are first converted into propargyl ammonium salts,followed by a base-promoted[2,3]-sigmatropic rearrangement.This one-pot,two-step reaction proceeds in the absence of transition metals,displays a very broad scope,and does not require the introduction of the electron-withdrawing group into the starting materials.

1D Fe3O4@CuSiO3 composites catalyzed decarboxylative A^3-coupling for propargylamine synthesis

Highly active and stable magnetic copper catalysts were successfully achieved by magnetic induced Stober method and subsequent hydrothermal reaction with copper ions in alkaline condition.The high content of Cu2+as well as the unique structures of hierarchical copper silicate in the as-prepared catalysts endowed their outstanding catalytic performance.Efficient decarboxylative A3-coupling of a-keto acid,amine and alkyne was realized with the low Fe3 O4@CuSiO3 loading.A range of propargylamines were produced in good to excellent yields under solvent-free condition.Moreover,the catalyst can be easily separated from the final organic product with an external magnet.Also,this kind of catalyst could be recycled up to six times while maintaining its activity.

Ag_(2)CO_(3)-catalyzed efficient synthesis of internal or terminal propargylicamines and chalcones via A^(3)-coupling under solvent-free condition

Several simple, fast and practical protocols have been developed to synthesize internal or terminal propargylamines and chalcones via A^(3)-coupling reaction of aldehydes, amines, and alkynes catalyzed by an easily available catalyst Ag_(2)CO_(3)under solvent-free condition. The reaction proceeded smoothly to deliver various products in good-to-excellent yields with good functional group tolerance. Gram-scale preparation, bioactive molecule synthesis and asymmetric substrates have been demonstrated. Furthermore,plausible mechanisms for the synthesis of different products have been proposed.

One-pot synthesis of N-aryl propargylamine from aromatic boronic acid,aqueous ammonia,and propargyl bromide under microwave-assisted conditions

A facile,one-pot synthesis of N-aryl propargylamine from aromatic boronic acid,aqueous ammonia,and propargyl bromide has been achieved under microwave-assisted conditions.The reactions can be smoothly completed within a total 10 min through a two-step procedure,including copper-catalyzed coupling of aromatic boronic acids with aqueous ammonia and following propargylation by propargyl bromide.

The Lewis Acid-promoted Novel Cyclization Reactions Towards N-adn O-Containing Heterocycles

1 Results Nitrogen and oxygen-containing heterocyclic systems are important structures in organic chemistry because of their presence in many biologically active compounds.In this work,a new zinc and indium-promoted conjugate addition-cyclization reaction to afford nitrogen and oxygen-containing five-membered heterocycles has been developed.A Lewis acid-catalyzed cyclization of an ethenetricarboxylate derivative with propargylamines or propargyl alcohols to give methylenepyrrolidines and methylenetetrah...