An efficient ‘on-water’ synthesis of 1,4-dihydropyridines using Fe3O4@SiO2 nanoparticles as a reusable catalyst

An ‘on-water’, efficient, high yielding, expeditious method has been developed for the synthesis of 1,4-dihydropyridine (1,4-DHP) derivatives via an one-pot multi-component condensation of dimedone or 4-hydroxycoumarine, aldehydes, and ammonium acetate using Fe₃O₄@SiO₂ nanoparticles as a recyclable heterogeneous catalyst. This method takes advantage of the fact that water, a green solvent is used in combination with Fe₃O₄@SiO₂ nanoparticles as catalyst which can be easily recovered magnetically and reused for further runs.     

Kinetics of Iterative Carbohydrate Transfer to Polysaccharide Catalyzed by Chondroitin Polymerase on a Highly Sensitive Flow‐Type 27 MHz Quartz‐Crystal Microbalance

Using a highly sensitive flow‐type 27 MHz quartz crystal microbalance, we could detect a small mass change during stepwise and alternating one‐sugar transfer of glucuronic acid (GlcA) and N‐acetylgalactosamine (GalNAc) to an acceptor, catalyzed by chondroitin polymerase from Escherichia coli strain K4 (K4CP), and analyze the elongation mechanism of K4CP. K4CP was found to bind strongly to a chondroitin acceptor (K_d=0.97 μM ). Although the binding affinity and the catalytic rate constant for each monomer were considerably different, the apparent catalytic efficiency (k_cat/K_m) was similar (6.3×10⁴ M ^?1 s^?1 for GlcA transfer and 3.4×10⁴ M ^?1 s^?1 for the GalNAc transfer). This is reasonable for the smooth alternating elongation of GlcA and GalNAc on the acceptor. This is the first study to report the determination of kinetic parameters for enzymatic, alternated, sugar elongation.     

One-pot synthesis of cis-bis(2,2′-bipyridine)carbonylruthenium(II) complexes from a carbonato precursor: X-ray crystal structures and electron transfer processes of the series complexes

The reaction of Brønsted acids with cis-[Ru(bpy)₂(CO₃)] (bpy?=?2,2′-bipyridine) under CO results in cleavage of the carbonato ligand and formation of cationic cis-[Ru(bpy)₂(CO)L] ^{n +} complexes [L?=?ONO₂ (1 ⁺), OH₂ (2 ²⁺), Cl (3 ⁺), OCOH (4 ⁺), and OCOCH₃ (5 ⁺)]. The structures of 1 ⁺ and 2 ²⁺ were confirmed by single-crystal X-ray diffraction. Crystal data for 1(PF₆): monoclinic, P2₁/c, a?=?10.5242(3), b?=?15.4727(3), c?=?14.6571(3) Å, β?=?92.3219(9)°, V?=?2384.77(9) ų, Z?=?4, D _calcd?=?1.806?g cm^?3, 5460 unique reflections (R _int?=?0.032), R ₁?=?0.0540 [I?>?2σ(I)], wR ₂?=?0.1642 (all reflections); crystal data for 2(ClO₄)₂?·?H₂O: monoclinic, C2/c, a?=?20.4247(7), b?=?10.0777(3), c?=?15.6039(5) Å, β?=?127.7569(8)°, V?=?2539.31(14) ų, Z?=?4, D _calcd?=?1.769?g cm^?3, 2895 unique reflections (R _int?=?0.036), R ₁?=?0.0343 [I?>?2σ(I)], wR ₂?=?0.0907 (all reflections). Except for 2(PF₆)₂ the complexes exhibit oxidation at 1.02–1.30?V versus Fc⁺/Fc in acetonitrile. Bipyridine-centered reductions are also observed; these redox potentials depend on the nature of L. This convenient synthesis will be useful for producing cis-[Ru(bpy)₂(CO)L] ^{n +}-type complexes in high yield.     

Synthesis of novel ferrocene-containing 1,3-thiazinan-2-imines: One-pot reaction promoted by ultrasound irradiation

A simple one-pot synthesis of new ferrocene-containing 1,3-thiazinan-2-imines from 3-arylamino-1-ferrocenylpropan-1-ols and phenyl isothiocyanate has been developed. The key intermediate β-hydroxy thioureas were generated in situ using ultrasound irradiation and subsequent cyclization was achieved by the addition of acetic acid. The scope of the reaction towards various 3-arylamino-1-ferrocenylpropan-1-ols has been explored and the corresponding 3-aryl-6-ferrocenyl-N-phenyl-1,3-thiazinan-2-imines were obtained in moderate to high yields (52–90%).     

Pd-基金属-酸-碱多功能催化剂的制备及其丙酮一步法合成MIBK性能研究

甲基异丁基酮 (MIBK) 是一种重要的化学品, 广泛应用于涂料以及有机合成领域, 下游产品包括特种涂料溶剂、高品质脱蜡溶剂和高性能橡胶防老剂等. 近年来随国民经济的快速发展, 甲基异丁基酮的年需求量与价格逐年上升, 应用领域也不断拓宽. 因此, 开展 MIBK 绿色合成工艺的研究对提高原子经济性、打破国际技术壁垒以及满足国内市场需求具有重要意义. 目前生产 MIBK 最绿色、高效的生产方法是丙酮一步法, 包括缩合、脱水以及加氢等一系列反应过程, 该工艺顺利实施的关键在于所使用的催化剂. 根据丙酮一步法合成 MIBK 反应特点, 所用催化剂表面必须具备多种催化活性中 心, 从而保证缩合、脱水以及加氢反应的顺利进行, 实现从反应物到产物的高效转化. 因此, 高活性和高选择性多功能催化剂的制备是提高 MIBK 生产效率的有效途径.本文采用浸渍法将具有加氢活性的贵金属 Pd 负载在表面具有丰富酸性位点或碱性位点的固体酸或固体碱氧化物载体上, 制备了 Pd/MOx(M = Ti, Ce, Al, Si, La, Ca和Mg) 双功能催化剂, 并用于丙酮一步法合成 MIBK 反应中. 结果表明, Pd基金属-酸/碱双功能催化剂均可以催化该连串反应的进行, 其性能高于 Pd 基金属-酸双功能催化剂, 其中 Pd/MgO 催化剂上丙酮转化率为30.67%, MIBK 产率可达27.61%. 构效关系研究显示, 催化剂表面酸性位点和碱性位点对于该连串反应的各反应步骤催化性能有所不同, 其中碱性位点有利于丙酮缩合反应, 而酸性位点有利于二丙酮醇脱水反应, 且强路易斯碱性中心位点可以更好的催化缩合反应的进行, 同时中强度路易斯酸性中心位点具有最佳的催化脱水反应的能力. 此外, 表面具有最强路易斯碱性中心位点 Pd/La2O3催化剂并未表现出最高的MIBK产率, 说明在丙酮一步法合成MIBK反应中, Pd基双功能催化剂表面各位点间的协同对其催化性能具有重要的影响.本文进一步采用水热法和沉淀沉积法制备了系列MgTiOx、MgAlOx和CaTiOx二元复合氧化物 (MMO) 以及 CaMgAlOx和 TiMgAlOx三元MMO, 并以其为载体, 通过浸渍焙烧还原制备 Pd 基多功能催化剂, 并用于丙酮一步法合成MIBK反应中,发现Pd/MgAl-MMO多功能催化剂具有最高的催化活性及 MIBK 产率. 对其表面多功能位点数量进行调变, 并通过 XRD、CO2-TPD、NH3-TPD、吡啶红外、CO2红外和HRTEM等进行表征, 结果表明, 经过450 ℃焙烧酸碱中心摩尔量比为0.4的0.1%Pd/Mg3Al-MMO多功能协同催化剂三种催化活性中心位点协同作用最佳, 其丙酮转化率为38.20%, MIBK产率可达31.63%. Pd/Mg3AlMMO多功能协同催化剂三种活性位点接近性研究表明, 在多功能催化剂中分离酸中心活性位点、碱中心活性位点以及加氢活性位点后, 获得的双功能催化剂产率均明显下降, 说明Pd/Mg3Al-MMO多功能催化剂在三种活性位点相互接近时才能更好催化反应的进行. 根据多功能催化剂构效关系研究结果, 对各催化活性中心的密度及分布进行调控, 结果显示, 通过沉淀沉积法制备的Pd/Mg3Al-MMO催化剂性能进一步提高, 丙酮转化率为42.11%, 产率高达37.20%.     

One-pot,microwave-assisted synthesis of polymethylene-bridged bis(1H-1,2,4-triazol-5(3)-amines) and their tautomerism

A highly selective and efficient method for the synthesis of 3,3′(5,5′)-polymethylene-bis(1H-1,2,4-triazol-5(3)-amines) was developed using the reaction of dicarboxylic acids and aminoguanidine in an aqueous medium. This one-pot, microwave-promoted method was proved to be scalable affording the desired products in good yields and purity. The scope of the method was successfully explored by the preparation of a small library of polymethylene-bis(1H-1,2,4-triazol-5(3)-amines) with different alkyl chain linkers. The annular prototropic tautomerism in the prepared compounds was studied using NMR spectroscopy and X-ray crystallography.     

A Diazido Mannose Analogue as a Chemoenzymatic Synthon for Synthesizing Di‐N‐acetyllegionaminic Acid‐Containing Glycosides

A chemoenzymatic synthon was designed to expand the scope of the chemoenzymatic synthesis of carbohydrates. The synthon was enzymatically converted into carbohydrate analogues, which were readily derivatized chemically to produce the desired targets. The strategy is demonstrated for the synthesis of glycosides containing 7,9‐di‐N‐acetyllegionaminic acid (Leg5,7Ac₂), a bacterial nonulosonic acid (NulO) analogue of sialic acid. A versatile library of α2‐3/6‐linked Leg5,7Ac₂‐glycosides was built by using chemically synthesized 2,4‐diazido‐2,4,6‐trideoxymannose as a chemoenzymatic synthon for highly efficient one‐pot multienzyme (OPME) sialylation followed by downstream chemical conversion of the azido groups into acetamido groups. The syntheses required 10 steps from commercially available d ‐fucose and had an overall yield of 34–52 %, thus representing a significant improvement over previous methods. Free Leg5,7Ac₂ monosaccharide was also synthesized by a sialic acid aldolase‐catalyzed reaction.     

6,6′-Thiobis(methylene)-β-cyclodextrin dimer as a dimeric host and reusable promoter for synthesis of chromenones in water

Herein, two unit of β-cyclodextrin linked by thiomethylene bridge was synthesized and employed as a novel efficient supramolecular host for the synthesis of biologically active chromenones templates via three-component single-pot reaction. A possible reaction mechanism through molecular complexation is suggested based on 2D ROESY NMR spectroscopic analysis. Moreover, the catalyst could be easily recycled, while a 94% yield and 89% rate of catalyst recovery could be achieved after four cycles of catalyst recycling. Environmentally benign reaction conditions, excellent yields, and avoidance of organic solvent and conventional isolation as well as purification are the noteworthy credits of this developed protocol.     

Cu(I)-catalyzed one-pot reactions of isatins,indoles, and amines toward unsymmetrically substituted 2-carbonylarylureas

A series of unsymmetrical arylureas was obtained by the one-pot method for reacting isatins with indoles incorporating primary amino moieties, a significant heterocyclic skeleton for diverse pharmaceutically active structures. The reaction proceeds through Cu(I)-catalyzed C2C3 bond of the ring-opening isatins and then expands the substrates in the optimum conditions. Furthermore, selected compounds 4b and 4k exhibit moderate to good anti-schistosomicidal activities.     

Transition-metal-free,atom-economical cascade synthesis of novel 2-sulfonated-benzo[f][1,7]naphthyridines and their cytotoxic activities

An efficient, transition-metal-free cascade synthetic method has been developed for new 2-aryl/heteroaryl sulfonated benzo[f][1,7]naphthyridines. It is tert-butyl hydroperoxide (TBHP) mediated highly regioselective sulfonylation?cyclization?aromatization process between N-(3-aryl/heteroarylprop-2-yn-1-yl)quinolin-3-amines and aryl/heteroaryl sulfonylhydrazides. This synthetic protocol offers one-step strategy for CS and CC bond formations with a broad range of functional group tolerance. It is a simple, mild, and atom-economical route for the synthesis of various valuable functionalized 1, 2-aryl/heteroaryl sulfonated benzo[f][1,7]naphthyridines in moderate yields. Since the core motif of 2-sulfonated benzo[f][1,7]naphthyridines are biologically and pharmaceutically important (TLR activity 7, 8 modulators). Additionally, the synthesized derivatives were evaluated for their in vitro cytotoxic activities against six human cancer cell lines including lung (NCIH23), colon (HCT15), gastric (NUCG-3), renal (ACHN), prostate (PC-3), and breast (MDA-MB-231) cell lines. These compounds displayed significant cytotoxic activities against all tested human cancer cell lines.