52148-89-7Relevant articles and documents
A luminescent dye@MOF platform: Emission fingerprint relationships of volatile organic molecules
Dong, Ming-Jie,Zhao, Min,Ou, Sha,Zou, Chao,Wu, Chuan-De
, p. 1575 - 1579 (2014)
Self-assembly of luminescent moieties into porous metal-organic frameworks (MOFs) has generated many luminescent platforms for probing volatile organic molecules (VOMs). However, most of those explored thus far have only been based on the luminescence intensity of one transition, which is not efficient for probing different VOMs. We have synthesized a luminescent MOF material containing 1D nanotube channels, and further developed a luminescent dye@MOF platform to realize the probing of different VOMs by tuning the energy transfer efficiency between two different emissions. The dye@MOF platform exhibits excellent fingerprint correlation between the VOM and the emission peak-height ratio of ligand to dye moieties. The dye@MOF sensor is self-calibrating, stable, and instantaneous, thus the approach should be a very promising strategy to develop luminescent materials with unprecedented practical applications. Got the glow: A 3D coordination network with large hexagonal nanotube channels based on 1D infinite rod-shaped metal-carboxylate chains is reported. This material can absorb Rhodamine B dye into its pores to form a luminescent platform for visually probing different small molecules. Copyright
Mizoroki-Heck Reaction of Unstrained Aryl Ketones via Ligand-Promoted C-C Bond Olefination
Wang, Mei-Ling,Xu, Hui,Li, Han-Yuan,Ma, Biao,Wang, Zhen-Yu,Wang, Xing,Dai, Hui-Xiong
supporting information, p. 2147 - 2152 (2021/04/05)
Mizoroki-Heck reaction of unstrained aryl ketone with acrylate/styrene is accomplished via palladium-catalyzed ligand-promoted C-C bond cleavage. Various (hetero)aryl ketones are compatible in the reaction, affording the alkene product in good to excellent yields. Further applications in the late-stage olefination of some drugs, natural products, and fragrance-derived aryl ketones demonstrate the synthetic utility of this protocol. By employing ketone as both the directing group and the leaving group, 1,2-bifunctionalization is achieved via sequential ortho-C-H alkylation/ipso-Heck olefination.
Synthesis and Catalytic Applications of [N,N]-Pyrrole Ligands for the Regioselective Synthesis of Styrene Derivatives
Hochberger-Roa, Frank,Cortés-Mendoza, Salvador,Gallardo-Rosas, David,Toscano, Ruben A.,Ortega-Alfaro, M. Carmen,López-Cortés, José G.
supporting information, p. 4055 - 4064 (2019/07/31)
We report the synthesis of two [N,N]-donor ligands (5 a–b) containing a 2-chalcogenazoline as the structural motif. These compounds were synthesized from a common intermediate Fischer type aminocarbene complex (3). The palladium-complexes of these [N,N]-donor ligands were successfully used as catalytic precursors in the Mizoroki-Heck coupling reaction between aryl halides and methyl acrylate, styrene and ethylene. For methyl acrylates, high yields with TOF values between 0.6 and 5.5×105 h?1 were obtained. In the case of ethylene, we reached high regioselectivities to obtain a diversity of styrene derivatives under soft pressure conditions, with good values of TON and TOF. (Figure presented.).
Phosphetane oxides as redox cycling catalysts in the catalytic wittig reaction at room temperature
Longwitz, Lars,Spannenberg, Anke,Werner, Thomas
, p. 9237 - 9244 (2019/10/08)
Recently, phosphorus redox cycling has gained significant importance for a number of transformations originally requiring the use of stoichiometric amounts of phosphorus reagents. While these methodologies have several benefits, high catalyst loadings (≥10 mol percent) and harsh reaction conditions (T ≥ 100 °C) often limit their versatility and applicability. Herein, we report differently substituted phosphetane oxides as efficient catalysts for the catalytic Wittig reaction. The phosphetane scaffold is easy to modify, and a number of catalysts can be obtained in a simple two-step synthesis. The activity in the Wittig reaction significantly surpasses previously reported phospholane-based catalysts and the reaction can be conducted with catalyst loadings as low as 1.0 mol percent even at room temperature. Furthermore, a Br?nsted acid additive is no longer required to achieve high yields at these mild conditions. A methyl-substituted phosphetane oxide was employed to synthesize 25 different alkenes with yields of up to 97percent. The methodology has a good functional group tolerance and the reaction can be performed starting with alkyl chlorides, bromides, or iodides. Additionally, it was possible to use poly(methylhydrosiloxane) as the terminal reductant in the catalytic Wittig reaction employing 2-MeTHF as a renewable solvent. The intermediates of the Wittig reaction were analyzed by 31P NMR spectroscopy, and in situ NMR experiments confirmed phosphane oxide as the resting state of the catalyst. Further kinetic investigations revealed a striking influence of the base on the rate of phosphane oxide reduction.
Utilization of Synthetic Calcium-Phyllosilicates as Bifunctional Bases in the Matsuda-Heck Reaction
Brunner, Heiko,Vedder, Lennart
, p. 698 - 702 (2019/01/04)
Calcium-phyllosilicates can successfully be used as novel bases in the Matsuda-Heck reaction using methanol as solvent. The new experimental set-up distinguishes itself by higher reactivity and better selectivity compared to other systems.
Palladium nanoparticles immobilized on halloysite nanotubes covered by a multilayer network for catalytic applications
Massaro, Marina,Colletti, Carmelo G.,Buscemi, Gabriella,Cataldo, Salvatore,Guernelli, Susanna,Lazzara, Giuseppe,Liotta, Leonarda F.,Parisi, Filippo,Pettignano, Alberto,Riela, Serena
supporting information, p. 13938 - 13947 (2018/08/21)
The synthesis of pure fine chemicals for industrial purposes is one of the most attractive challenges of chemical research. The use of catalytic pathways mediated by palladium nanoparticles (PdNPs) for C-C bond formation is a useful way to obtain these kinds of compounds. To achieve this objective, the PdNPs can be efficiently loaded on a functionalized natural nanostructured support such as halloysite nanotubes (HNTs). Hybrid materials based on thiol functionalized halloysite nanotubes and highly cross-linked imidazolium salts were successfully developed and used for the stabilization of PdNPs. The HNT/Pd hybrids were thoroughly characterized from a physico-chemical point of view and tested as a catalyst in the Suzuki and Heck C-C coupling reactions under microwave irradiation to obtain innovative materials for fine chemicals synthesis. Catalytic tests highlighted the fact that the HNT/Pd hybrids show high performance and full recyclability (up to ten cycles) in both reactions. Regarding the Suzuki reaction, under the best experimental conditions, the remarkable values of a turnover number of 194?000 and a turnover frequency of 3?880?000 h-1 were achieved without metal contamination in the final products.
Selective Palladium-Catalyzed Carbonylation of Alkynes: An Atom-Economic Synthesis of 1,4-Dicarboxylic Acid Diesters
Liu, Jiawang,Dong, Kaiwu,Franke, Robert,Neumann, Helfried,Jackstell, Ralf,Beller, Matthias
supporting information, p. 10282 - 10288 (2018/08/03)
A class of novel diphosphine ligands bearing pyridine substituents was designed and synthesized for the first time. The resulting palladium complexes of L1 allow for chemo- and regioselective dialkoxycarbonylation of various aromatic and aliphatic alkynes affording a wide range of 1,4-dicarboxylic acid diesters in high yields and selectivities. Kinetic studies suggest the generation of 1,4-dicarboxylic acid diesters via cascade hydroesterification of the corresponding alkynes. Based on these investigations, the chemo- and regioselectivities of alkyne carbonylations can be controlled as shown by switching the ligand from L1 to L3 or L9 to give α,β-unsaturated esters.
Arylhydrazones Derivatives Containing a Benzothiazole Moiety, Efficient Ligands in the Palladium-Catalyzed Mizoroki–Heck and Suzuki–Miyaura Cross-coupling Reactions under IR Irradiation
Ortega-Jiménez, Fernando,Penieres-Carrillo, José Guillermo,López-Cortés, José Guadalupe,Carmen Ortega-Alfaro,Lagunas-Rivera, Selene
, p. 1881 - 1888 (2017/09/12)
A simple arylhydrazone containing the benzothiazole moiety which may be used as an efficient ligand in the palladium-catalyzed Mizoroki–Heck and Suzuki–Miyaura cross-coupling reactions, under infrared irradiation as an alternative source of energy, is presented. The reactions proceeded with extremely high efficiency under mild conditions and produced very good yields.
Noble metal-free catalytic decarboxylation of oleic acid to n-heptadecane on nickel-based metal-organic frameworks (MOFs)
Yang,McNichols,Davidson,Schweitzer,Gómez-Gualdrón,Trewyn,Sellinger,Carreon
, p. 3027 - 3035 (2017/08/01)
Nickel based metal organic frameworks (Ni-MOFs) were successfully synthesized using new conjugated carboxylic acid linkers. These conjugated carboxylic acid linkers were synthesized using mild Heck coupling that led to the incorporation of functional groups not possible by traditional synthetic methods. Control of linker size allows for porosity tuning of the crystalline network and high surface area, that, in theory, results in the increased accessibility to Ni metal centers for catalysis. The resultant crystalline Ni-MOFs displayed BET areas as high as ～314 m2 g-1. To investigate their catalytic activity for conversion of oleic acid to liquid hydrocarbons, Ni-MOFs were grown on zeolite 5A beads that served as catalytic supports. The resultant catalysts displayed heptadecane selectivity as high as ～77% at mild reaction conditions, one of the highest yields for non-noble metal containing catalysts. The catalytic activity correlated to the concentration of acid sites. A slight decrease in catalytic activity was observed after catalysts recycling.
An in Situ Generated Palladium on Aluminum Oxide: Applications in Gram-Scale Matsuda-Heck Reactions
Pape, Simon,Dauk?ait?, Lauryna,Lucks, Sandra,Gu, Xiaoting,Brunner, Heiko
supporting information, p. 6376 - 6379 (2016/12/23)
In situ generated palladium on aluminum oxide provides an active catalytic system for Matsuda-Heck reactions in gram-scale. The novel catalyst proceeded through a significantly higher catalytic activity compared to the classical Pd/C system. Based on the high catalytic activity the first α,β,β-triarylation of methyl acrylate in good yields could be provided in one-step.
