Construction of an Asymmetric Porphyrinic Zirconium Metal-Organic Framework through Ionic Postchiral Modification.

Herein, one kind of neutral chiral zirconium metal-organic framework (Zr-MOF) was reported from the porphyrinic MOF (PMOF) family with a metallolinker (MnIII-porphyrin) as the achiral polytopic linker [free base tetrakis(4-carboxyphenyl)porphyrin] and chiral anions. Achiral Zr-MOF was chiralized through the exchange of primitive anions with new chiral organic anions (postsynthetic exchange). This chiral functional porphyrinic MOF (CPMOF) was characterized by several techniques such as powder X-ray diffraction, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, 1H NMR, energy-dispersive X-ray spectroscopy, scanning electron microscopy, and Brunauer-Emmett-Teller measurements. In the resulting structure, there are two active metal sites as Lewis acid centers (Zr and Mn) and chiral species as Brønsted acid sites along with their cooperation as nucleophiles. This CPMOF shows considerable bimodal porosity with high surface area and stability. Additionally, its ability was investigated in asymmetric catalyses of prochiral substrates. Interactions between framework chiral species and prochiral substrates have large impacts on the catalytic ability and chirality induction. This chiral catalyst proceeded asymmetric epoxidation and CO2 fixation reactions at lower pressure with high enantioselectivity due to Lewis acids and chiral auxiliary nucleophiles without significant loss of activity up to the sixth step of consecutive cycles of reusability. Observations revealed that chiralization of Zr-MOF could happen by a succinct strategy that can be a convenient method to design chiral MOFs.

Multicomponent reactions of ammonium thiocyanate, acyl chlorides, alkyl bromides, and enaminones: a facile one-pot synthesis of thiophenes.

An efficient synthesis of thiophene derivatives is described via one-pot reaction between ammonium thiocyanate, acyl chlorides, α-halocarbonyls, and enaminones under solvent-free conditions at 65 °C. The mild reaction conditions and high yields of the products exhibit the good synthetic advantage of these methods.

High performance of ultrasonic-assisted synthesis of two spherical polymers for enantioselective catalysis.

Chiral polymers have aroused great attention in among chiral supramolecular materials based on their features. Herein, for the first time, the synthesis of chiral polymeric composites (CMNPs/1,4-Zbtb & 1,3-Zbtb) have been reported with entrapment through three strategies: ultrasonic irradiation, solvothermal, and mechanical stirring. According to the obtained results, it is found that ultrasound-assisted synthesis can be considered as an inexpensive and efficient method than the others, from the point ofviewof energy and time consuming. In this strategy, encapsulation of chiral magnetic nanoparticles (CMNPs) by using tetrazole-based polymers (Zbtbs) happens, in-situly. These chiral sphere-like inorganic-organic polymers can be considered as core and shell composites with catalytic activity due to their acidic (semi unsaturated Zn: open metal sites) and basic (abundant basic nitrogens) centers. In these structures, the unprecedented chirality induction can happen from the core to shell by non-covalent interaction, easily. They could catalyze symmetric oxidation and asymmetric henry condensation to give chiral ß-nitroalkanol. Circular dichroism and chiral gas chromatography were used to characterize the produced enantiomers. These chiral polymeric materials can be considered as unique acid-base bifunctional catalysts with efficient properties such as high stability, enantiomeric excess, enantioselectivity to the main product, and protecting from CMNPs leaching.