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Relevant academic research and scientific papers

Zirconium triflate grafted on SBA-15 as a highly efficient solid acid catalyst for ring opening of epoxides by amines and alcohols

Metal (Al, Ti, Zr) triflate grafted mesoporous SBA-15 (AlTf/S, TiTf/S, ZrTf/S) samples were synthesized as inexpensive solid acid materials by a simple one-pot-two-step synthesis methodology. These materials were characterized by X-ray diffraction, N2-sorption, thermogravimetric analysis, Fourier transform infrared spectroscopy (FT-IR), in-situ pyridine FT-IR spectroscopy, and elemental analysis. ZrTf/S was found to be a highly efficient and reusable solid acid catalyst for ring opening of epoxides with amines and alcohols and produced β-amino alcohols and β-alkoxy alcohols respectively under ambient reaction conditions. The ZrTf/S catalyst showed the highest activity, which was attributed to its high acidity compared with that of the Ti and Al containing samples.

A Thiophene-2-carboxamide-Functionalized Zr(IV) Organic Framework as a Prolific and Recyclable Heterogeneous Catalyst for Regioselective Ring Opening of Epoxides

A new thiophene-2-carboxamide-functionalized Zr-UiO-66 MOF (1) was synthesized by employing a traditional solvothermal procedure. Compound 1 displayed high thermal (up to 340 °C under an Ar atmosphere) and chemical stability (in water, 1 M HCl, and acetic acid). A nitrogen physisorption measurement with the activated form of 1 (denoted 1) exhibited a BET surface area (781 m2/g) despite attachment of a bulky side chain with the linker molecule. Compound 1 was able to heterogeneously catalyze the ring-opening reaction of epoxides with amines. Catalyst 1 exhibited significant yields as well as wide substrate scope in the ring opening of epoxides by means of amines. It also displayed better catalytic performance in comparison to known MOF catalysts such as Cu3(BTC)2, Fe(BTC) (BTC: 1, 3, 5-benzenetricarboxylate), and Zr-UiO-66. Control experiments were performed with free linker, Zr(IV) salt and without catalyst 1, confirming the exclusive role of 1 in the catalytic reaction. The reusability characteristics of catalyst 1 was established for up to five consecutive catalytic cycles. The synthesis and characterization of the linker molecule, material 1, and 1 and mechanism of the catalysis reaction were studied elaborately.

Design and assembly of a chiral composite metal-organic framework for efficient asymmertric sequential transformation of alkenes to amino alcohols

In this work, we report the successful construction of two chiral porous metal-metallosalan frameworks (1 and 2) by using dipyridylfunctionalized chiral Al(salen) and Mn(salen) separately, and then a composite crystal MOF 3 was constructed with 1 inside, which was encapsulated by 2 outside. The resulting composite crystal appeared to be highly enantioselective for the alkene epoxidation/epoxide aminolysis reactions with a maximum ee of 97%.

Post-synthesis of Zr-MOR as a robust solid acid catalyst for the ring-opening aminolysis of epoxides

Zirconosilicate with the MOR topology (Zr-MOR) was successfully prepared using a two-step post-synthesis strategy from pre-dealumination of a H-MOR zeolite and subsequent dry impregnation of Cp2ZrCl2. The incorporated Zr species main

Heterogeneous ring-opening reactions and Knoevenagel condensation reactions with cobalt complexes: Effect of CoII versus CoIII states on catalysis

This work illustrates comparative catalytic performance of two sets of cobalt complexes within a common macrocyclic ligand environment: CoII complexes 1 and 2 versus CoIII complexes 3 and 4. All four cobalt complexes functioned as the heterogeneous catalysts for the ring-opening reactions of assorted epoxides as well as Knoevenagel condensation reactions of assorted aldehydes. Cobalt(II) complexes were noted to be the superior catalysts over cobalt(III) complexes for both types of organic transformations. The observed difference in the catalytic performance of two sets of cobalt complexes has been related to the kinetic differences between CoII versus CoIII ions. All four cobalt complexes display high catalytic efficiency and excellent reusability without any apparent loss in the catalytic performance.

Multivariate Metal-Organic Frameworks as Multifunctional Heterogeneous Asymmetric Catalysts for Sequential Reactions

The search for versatile heterogeneous catalysts with multiple active sites for broad asymmetric transformations has long been of great interest, but it remains a formidable synthetic challenge. Here we demonstrate that multivariate metal-organic frameworks (MTV-MOFs) can be used as an excellent platform to engineer heterogeneous catalysts featuring multiple and cooperative active sites. An isostructural series of 2-fold interpenetrated MTV-MOFs that contain up to three different chiral metallosalen catalysts was constructed and used as efficient and recyclable heterogeneous catalysts for a variety of asymmetric sequential alkene epoxidation/epoxide ring-opening reactions. Interpenetration of the frameworks brings metallosalen units adjacent to each other, allowing cooperative activation, which results in improved efficiency and enantioselectivity over the sum of the individual parts. The fact that manipulation of molecular catalysts in MTV-MOFs can control the activities and selectivities would facilitate the design of novel multifunctional materials for enantioselective processes.

Greener aminolysis of epoxides on BiCl3/SiO2

The remarkable catalytic activity of BiCl3/SiO2 for the ring-opening of epoxides with aromatic and aliphatic amines under microwave and thermal heating was observed. This eco-friendly heterogeneous catalyst displayed high to excellent regioselectivity in the synthesis of β-amino alcohols under solvent-free conditions. High turnover frequency (TOF) values under microwave heating and excellent reusability of the catalyst may significantly contribute to applied chemistry.

Mesoporous Zr-Beta zeolites prepared by a post-synthetic strategy as a robust Lewis acid catalyst for the ring-opening aminolysis of epoxides

Mesoporous zirconosilicate, stannosilicate, and titanosilicate with the BEA structure framework have been prepared from the commercially available Beta zeolite via acid-alkaline treatments and subsequent dry impregnation of appropriate organometallic prec

Manganese Complexes of Pyrrole- and Indolecarboxamide Ligands: Synthesis, Structure, Electrochemistry, and Applications in Oxidative and Lewis-Acid-Assisted Catalysis

This work shows the synthesis and structural, spectroscopic, and electrochemical properties of MnIII complexes supported with pyrrole- and indolecarboxamide ligands. In all cases, the respective ligand constitutes a N4 coordination sphere about the MnIII ion. The MnIII complexes of pyrrolecarboxamide ligands are square pyramidal with a fifth Cl atom, whereas analogous complexes of indolecarboxamide ligands are essentially square planar. Electrochemical studies reveal highly negative MnIII/II and moderately positive MnIV/III redox potentials. In situ generated Mn4+ species of the pyrrolecarboxamide ligands were characterized by absorption and electron paramagnetic resonance spectroscopy. All complexes functioned as catalysts in olefin epoxidation reactions by using PhIO as the oxo-transfer agent. All complexes also acted as Lewis acid catalysts for ring-opening reactions of assorted epoxides with various nucleophiles. We also show a one-pot, two-step epoxidation reaction followed by ring opening, which illustrates the catalytic significance of the present complexes. Importantly, MnIII complexes carrying electron-donating substituents on the ligand were found to be better catalysts.

Highly efficient nanocrystalline zirconosilicate catalysts for the aminolysis, alcoholysis, and hydroamination reactions

Nanocrystalline zirconosilicates and titanosilicates with MFI framework structure were hydrothermally synthesized by the addition of organosilanes in the synthesis composition of conventional zirconosilicate and titanosilicate materials. Materials were characterized by a complementary combination of X-ray diffraction, nitrogen sorption, scanning/transmission electron microscopy (S/TEM), ammonia temperature-programmed desorption (TPD), Fourier transform infrared (FT-IR) spectroscopy, and ultraviolet-visible (UV-vis) spectroscopic investigations. Nanocrystalline zeolite catalysts of the present study are reusable. They exhibit significantly higher catalytic activities in aminolysis and alcoholysis compared with the hitherto known catalysts. A range of β-amino alcohols/β-alkoxy alcohols with high regioselectivity were synthesized using zirconosilicates. Application of these materials was also extended in the synthesis of aminoesters by the hydroamination reaction of methyl acrylates and amines. Structure activity relationship was explained based on acidity measurements, reactivity of amines/alcohols, and adsorption of reactants on catalysts.