Metal-Organic Framework Derived Metal Oxide Clusters in Porous Aluminosilicates: A Catalyst Design for the Synthesis of Bioactive aza-Heterocycles

Martín, Nuria Nicodemus; Dusselier, Michiel; Vos, Dirk De; Cirujano, Francisco G.

doi:10.1021/acscatal.8b03908

Cited by 37 publications

(31 citation statements)

References 49 publications

(20 reference statements)

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“…The NiBDP@Cu MOF described previously, shows a much better performance (turnovers twice as high) than state‐of‐the‐art Ni/Cu catalysts in the Friedel‐Crafts alkylation of indole with β‐nitrostyrene . However, the use of Zn‐MOF‐5 as precursor of well‐dispersed ZnO in aluminosilicates, generates MOF derived metal oxides with turnovers two orders of magnitude higher than the parent MOF . Moreover, homochiral Cu‐MOFs constructed from ( R )‐2,2′‐dihydroxy‐1,1′‐binaphthyl‐6,6′‐dicarboxylic acid and Cu(NO 3 ) 2 have been reported for the same reaction, obtaining high yields of the alkylated indole (82 %) with excellent enantioselectivities (90 % e.e.)…”

Section: Mofs and Enzymes As Catalysts For C−c Bond Formationsmentioning

confidence: 94%

Engineered MOFs and Enzymes for the Synthesis of Active Pharmaceutical Ingredients

Cirujano

2019

ChemCatChem

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The latest strategies in the design and synthesis of metalorganic frameworks as heterogeneous catalysts in organic synthesis are compared with biocatalyzed transformations, as a step forward to a more convenient industrial production of pharmaceuticals. Relevant CÀ C and CÀ N bond forming reactions that are both chemo-and bio-catalyzed by synthetic MOFs and in vitro evolved and/or promiscuous enzymes with the aim of obtaining key bioactive scaffolds in a sustainable, competitive and cost-efficient manner, are thoroughly discussed in this mini review.

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Section: Mofs and Enzymes As Catalysts For C−c Bond Formationsmentioning

confidence: 94%

Engineered MOFs and Enzymes for the Synthesis of Active Pharmaceutical Ingredients

Cirujano

2019

ChemCatChem

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“…Sn content (wt.%) SBET (m 2 g −1 ) Smicro (m 2 g −1 ) Sextra (m 2 g −1 ) Vtol (cm 3 g −1 ) Vmicro (cm 3 Figure 2 shows the UV-VIS spectra of Sn-containing catalysts with different matrixes (A) and the Sn-containing defective S-1 zeolite catalysts with different Sn loadings (B). So far, the UV-VIS spectroscopic technique has been widely used as an informative characterization method for Sn species in Sn-containing zeolites and molecular sieves [16].…”

Section: Samplementioning

confidence: 99%

“…Aluminosilicate zeolites are generally strongly acidized, and they belong to a big family that has already more than 200 different topologic structures so far [2]. However, the conversions of reactants with strong basicity such as nitrogen-containing compounds [3], which are useful reactions for the synthesis of functional organic molecules, often need zeolitic solid acids with mild acidity. One important example of this kind of reaction is the conversion of ethylenediamine (EDA) to heterocyclic amines like 1, 2-Diazabicyclo [2, 2, 2] octane (TEDA) and piperazine (PIP).…”

Section: Introductionmentioning

confidence: 99%

Effect of Stannic Species Modification on the Acidity of Silicalite-1 and Its Enhancement in Transforming Ethylenediamine to Heterocyclic Amines

et al. 2020

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In this study, a series of SnO 2 modified zeolite catalysts (Snx-S-1; x is the weight percentage of Sn) were prepared with SnCl 2 and a defective Silicalite-1 (S-1) zeolite via facile deposition-precipitation method. It was found that the stannic species modified all-silica zeolite catalysts were active for the intermolecular condensation of ethylenediamine (EDA) to 1, 2-Diazabicyclo [2, 2, 2] octane (TEDA) and piperazine (PIP). The best catalyst Sn6-S-1 (6 wt.% Sn loading) showed 86% EDA conversion and 93% total selectivity to TEDA and PIP. By contrast, the defective S-1 zeolite parent showed only approximately 9% EDA conversion under the same conditions. With the help of catalyst characterization techniques including hydroxyl vibration and pyridine adsorption FT-IR spectroscopy (transmission mode), the enhancement of the catalytic activity of the SnO 2 modified zeolite catalysts (Snx-S-1) was mainly attributed to the formation of mild Lewis acid sites in the siliceous zeolite. Both the hydroxyl nests of the defective S-1 zeolite and the dispersed SnO 2 clusters should be the important factors for the formation of mild Lewis acid sites on the modified zeolite. Based on the catalytic performance of the modified zeolite in the conversion of EDA to PIP and TEDA, it is inferred that the mildly acidified defective S-1 zeolite by the SnO 2 deposition modification might become a very active and durable catalyst for reactions involving strongly alkaline reactants and products.Catalysts 2020, 10, 211 2 of 16 hydroxyl groups) of H-ZSM-5 zeolite. For this reason, some modification methods such as alkali metal ion modification [7] and dealumination [9], etc. have been proposed to weaken the strength of acidic sites in H-ZSM-5. However, such efforts often cause negative effects such as worse diffusivity due to pore channel blocking. In 2003, titanium silicalite-1 (TS-1) was patented for the reaction of EDA to TEDA and PIP [10]. Later, people conducted a detailed study on the intermolecular condensation of EDA to make PIP and TEDA over TS-1 zeolite [11]. Silicalite-1 (S-1) zeolite is an aluminum-free crystalline silicate with the same MFI topological framework as the Al-containing ZSM-5 zeolite and Ti-containing silicate zeolite (TS-1). It is well known that the presence of defective sites in S-1 lattice can form mild acidity (silanol nests). The defective S-1 zeolite has been reported as an active Beckmann rearrangement catalyst [12][13][14][15]. However, previous study indicated that the defective S-1 zeolite itself was not very active and selective for the reaction of EDA to TEDA and PIP, giving only 19.5% EDA conversion and 7.5% TEDA selectivity [11]. This implies that the acidity of defective S-1 is too weak to be an efficient catalyst for the conversion of EDA.In recent years, Sn-β zeolite has attracted increasing attention because its isolated framework Sn is an active Lewis acid site for many reactions, including Baeyer-Villiger oxidation, sugar isomerization, and Meerwein-Ponndorf-Verley reaction [16,17]. Sn-MFI zeol...

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“…[31][32][33] Furthermore, MOFs are an interesting alternative to the use of co-precipitated bulk metal oxides due to the fact that the metal (oxide precursor) sites are atomically dispersed in a metal organic crystalline framework and thus, it should produce less agglomerated and smaller nanoparticles after thermal decomposition of the linker in the close vicinity of the zeolite. [34][35][36][37][38][39][40] Recently, some of the authors here used this concept to create Zn and Cu oxide clusters on FAU zeolites for CÀ C and CÀ N couplings during the synthesis of fine chemical intermediates. [34] Moreover, different groups have employed MOFs or MOF derived catalysts in the hydrogenation of CO into hydrocarbons (Fischer-Tropsch) and hydrogenation of CO 2 into methanol or methane.…”

Section: Introductionmentioning

confidence: 99%

“…[34][35][36][37][38][39][40] Recently, some of the authors here used this concept to create Zn and Cu oxide clusters on FAU zeolites for CÀ C and CÀ N couplings during the synthesis of fine chemical intermediates. [34] Moreover, different groups have employed MOFs or MOF derived catalysts in the hydrogenation of CO into hydrocarbons (Fischer-Tropsch) and hydrogenation of CO 2 into methanol or methane. [35][36][37][38][39][40] Here, we describe the possibility to use InÀ Zrbased MOFs as pre-catalysts in the presence of acid CHA zeolites, to yield truly bifunctional materials for the direct transformation of CO 2 into olefins (see (InÀ Zr) MOF /CHA in Figure 1).…”

Section: Introductionmentioning

confidence: 99%

MOF‐derived/zeolite hybrid catalyst for the production of light olefins from CO₂

et al. 2020

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In this contribution we propose an alternative catalytic system based on MOF derivatives and small pore zeolites for the selective conversion of CO 2 into light olefins, using the lowest metal loadings and highest GHSV reported in literature. The catalyst synthesis involves deriving InÀ Zr oxides from MOFs containing these metals in their structure, i. e. (Zr)UiO-67-bipy-In, via direct calcination in the presence of the zeolite, avoiding co-precipitation, washing and mixing steps. This effectively creates a truly bifunctional InÀ Zr zeolite catalyst, opposed to physical mixtures of two catalysts using different precursors. The good dispersion and low loadings of the MOF-derived InÀ Zr oxide supplemented with the strong acidity of chabazitetype zeolites allows to couple the activation of CO 2 with CÀ C coupling, obtaining space time yields of 0.1 mol of CO 2 converted to light olefins per gram of In per hour at 375°C, under the GHSV conditions employed.

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Metal-Organic Framework Derived Metal Oxide Clusters in Porous Aluminosilicates: A Catalyst Design for the Synthesis of Bioactive aza-Heterocycles

Cited by 37 publications

References 49 publications

Engineered MOFs and Enzymes for the Synthesis of Active Pharmaceutical Ingredients

Engineered MOFs and Enzymes for the Synthesis of Active Pharmaceutical Ingredients

Effect of Stannic Species Modification on the Acidity of Silicalite-1 and Its Enhancement in Transforming Ethylenediamine to Heterocyclic Amines

MOF‐derived/zeolite hybrid catalyst for the production of light olefins from CO₂

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Metal-Organic Framework Derived Metal Oxide Clusters in Porous Aluminosilicates: A Catalyst Design for the Synthesis of Bioactive aza-Heterocycles

Cited by 37 publications

References 49 publications

Engineered MOFs and Enzymes for the Synthesis of Active Pharmaceutical Ingredients

Engineered MOFs and Enzymes for the Synthesis of Active Pharmaceutical Ingredients

Effect of Stannic Species Modification on the Acidity of Silicalite-1 and Its Enhancement in Transforming Ethylenediamine to Heterocyclic Amines

MOF‐derived/zeolite hybrid catalyst for the production of light olefins from CO2

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MOF‐derived/zeolite hybrid catalyst for the production of light olefins from CO₂