Tandem Synthesis of Tetrasubstituted NH Pyrroles from Simple Nitriles

An efficient tandem route to obtain tetrasubstituted NH pyrroles in a one-pot manner has been developed, staring from simple nitriles, ethyl bromoacetates, and zinc. This reaction involves oxidative dimerization of the zinc bromide complex of β-enaminoesters using cerium ammonium nitrate (CAN) as an oxidant, affording 2,3,4,5-tetrasubstituted pyrroles in yields up to 91%.     

Cu2O-Catalyzed Conversion of Benzyl Alcohols Into Aromatic Nitriles via the Complete Cleavage of the C≡N Triple Bond in the Cyanide Anion

Nitrogen transfer from cyanide anion to an aldehyde is emerging as a promising method for the synthesis of aromatic nitriles. However, this method still suffers from a disadvantage that a use of stoichiometric Cu(II) or Cu(I) salts is required to enable the reaction. As we report herein, we overcame this drawback and developed a catalytic method for nitrogen transfer from cyanide anion to an alcohol via the complete cleavage of the C≡N triple bond using phen/Cu₂O as the catalyst. The present condition allowed a series of benzyl alcohols to be smoothly converted into aromatic nitriles in moderate to high yields. In addition, the present method could be extended to the conversion of cinnamic alcohol to 3-phenylacrylonitrile.     

An efficient synthesis of medicinally important indole based triarylmethanes by using propylphosphonic anhydride (T3P®)

Abstract

We have developed an economical and efficient method for the synthesis of medicinally and synthetically important indole-based triarylmethanes by using indoles and benzhydrols in the presence of propylphosphonic anhydride (T3P^®). This methodology is an alternate approach for the C–C bond formation with good to excellent yields. In this T3P-mediated dehydration approach, the by-product is highly soluble in water, so that it can be done at larger scale also. In addition to that this efficient protocol has several advantages such as mild reaction conditions, short reaction time and operational simplicity. We have successfully synthesized pyrrole, imidazothiadiazole and imidazolo pyridine based triarylmethanes also.     

KOtBu‐Catalyzed Michael Addition Reactions Under Mild and Solvent‐Free Conditions

Designed transition metal complexes predominantly catalyze Michael addition reactions. Inorganic and organic base‐catalyzed Michael addition reactions have been reported. However, known base‐catalyzed reactions suffer from the requirement of solvents, additives, high pressure and also side‐reactions. Herein, we demonstrate a mild and environmentally friendly strategy of readily available KO^tBu‐catalyzed Michael addition reactions. This simple inorganic base efficiently catalyzes the Michael addition of underexplored acrylonitriles, esters and amides with (oxa‐, aza‐, and thia‐) heteroatom nucleophiles. This catalytic process proceeds under solvent‐free conditions and at room temperature. Notably, this protocol offers an easy operational procedure, broad substrate scope with excellent selectivity, reaction scalability and excellent TON (>9900). Preliminary mechanistic studies revealed that the reaction follows an ionic mechanism. Formal synthesis of promazine is demonstrated using this catalytic protocol.     

3 d Transition Metal‐Catalyzed Hydrogenation of Nitriles and Alkynes

Selective hydrogenation of nitriles and alkynes is crucial considering the vast applications of reduced products in industries and in the synthesis of bioactive compounds. Particularly, the late 3d transition metal catalysts (manganese, iron, cobalt, nickel and copper) have shown promising activity for the hydrogenation of nitriles to primary amines, secondary amines and imines. Similarly, semihydrogenation of alkynes to E‐ and Z‐alkenes by 3d metals is adequately successful both via the transfer hydrogenation and by using molecular hydrogen. The emergence of 3d transition metals in the selective synthesis of industrially relevant amines, imines and alkenes makes this protocol more attractive. Herein, we provide a concise overview on the late 3d transition metal‐catalyzed hydrogenation of nitriles to amines and imines as well as semihydrogenation of alkynes to alkenes.     

氰基衍生化制备胺的研究进展

胺是有机分子中最常见且重要的结构之一,广泛存在于天然产物分子、药物、染料、塑料等的分子结构中,开发合成胺的有效方法在化学工业中具有很高的需求但仍充满挑战。在诸多已知有机胺的合成方法中,以氰基为前体还原衍生化制备胺被认为是一条原子经济且绿色可行的方案。然而,氰基中存在稳定的碳氮三重键,还原过程涉及较多中间体,而部分中间体活性比氰基更高,因此反应受还原剂、催化剂、反应条件的影响很大,由氰基选择性制备目标胺结构仍充满挑战。本文从氰基的基本电子结构与反应活性出发,综述了近年来以氰基为原料的官能团胺基化反应,对部分重要反应的催化剂和反应机理做了简要讨论,为设计氰基制胺催化剂和应用工艺提供了新的视角。     

Design of TiO2@graphene nanosheets with rough surface and its reinforcement to polyarylene ether nitriles

The interfacial interaction is extremely important when dealing with filler‐reinforced polymer materials. Herein, in order to improve the interfacial interaction with the polyarylene ether nitriles (PEN) matrix, a three‐dimensional rough structure was designed. First, needle‐like TiO₂ nanocrystals were grown on each surface of the graphene. Morphology analysis proved that rough TiO₂ nanocrystals were coated on the graphene nanosheets. Then, TiO₂@graphene/PEN composites were fabricated to investigate the filler–matrix interaction. Thereafter, the different polymer chains could be interlocked by the TiO₂ “needles” when the rough TiO₂@graphene was embedded into the polymer resin. The surrounding PEN polymer chains (work as ropes) could tie to the “needles” (work as wood pile). That is to say, the effective polymer chain length was greatly lengthened, resulting in the improvement of interfacial interactions and mechanical properties. Most importantly, the morphology, mechanical and rheological tests of the composites also proved the improvement of interfacial interactions and mechanical properties. Copyright © 2015 John Wiley & Sons, Ltd.     

Condensation of nitriles of polyhalogenated carboxylic acids and benzonitrile with 2-hydroxy-4,6-dimethylacetophenone

Condensation of 2-hydroxy-4,6-dimethylacetophenone with trifluoro- and trichloroacetonitriles gives 2-amino-5,7-dimethyl-2-trifluoro(trichloro)methyl-4-chromanones. The condensation with 2,2,3,3-tetrafluoropropionitrile, perfluorovaleronitrile, and benzonitrile stops at the stage of formation of the corresponding enamines. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 362–363, February, 1998.     

Synthesis,characterization and properties of multifunctional poly(arylene ether nitriles) (PEN)/CNTs/Fe3O4 nanocomposites

In this study, a novel multifunctional poly(arylene ether nitriles)(PEN)/carbon nanotubes/Fe₃O₄ nanocomposite with high tensile strength, magnetic, and electrical properties was investigated. First, we synthesized the monodisperse Fe₃O₄ nanoparticles on the surface of the multiwalled carbon nanotubes and then the hybrid material was compounded with PEN through the solution‐casting method. The SEM and TEM images indicated that the monodisperse Fe₃O₄ nanoparticles, with the diameters of 70∼80 nm, were self‐assembled along CNTs via the covalent bond method, which was confirmed by FTIR and XRD. The results of tensile properties showed that the tensile strength and modulus reached their highest values at the CNTs/Fe₃O₄ loading content of 1 wt % and both were greatly enhanced after heat treatment. Electrical conductivity of the polymer was dramatically enhanced at the low loading level of CNTs/Fe₃O₄; the electrical percolation of was in the range of 5∼8 wt % of CNTs/Fe₃O₄. The magnetic study showed that the saturation magnetization (M_s) of PEN/CNTs/Fe₃O₄ nanocomposites increased with the increase of CNTs/Fe₃O₄ loading content, and the coercive force (H_c) of the nanocomposite was independent of the CNTs/Fe₃O₄ content. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011