36681-66-0

Upstream product

• 513-81-5 2,3-dimethyl-buta-1,3-diene 
• 105-07-7 4-cyanobenzaldehyde 

Relevant academic research and scientific papers

Robust Corrole-Based Metal-Organic Frameworks with Rare 9-Connected Zr/Hf-Oxo Clusters

The corrole unit from the porphyrinoid family represents one of the most important ligands in the field of coordination chemistry, which creates a unique environment allowing for the observation of unusual electronic states of bound metal cations and has

CORROLE-BASED FRAMEWORKS AND METHODS OF USE THEREOF

Described herein are corrole-based frameworks and methods for making the same. The corrole-based frameworks have unique structural and physical properties, which lends them to be versatile in a number of different applications and uses such as in gas stor

AlCl3 catalyzed oxa-Diels-Alder reaction of aromatic aldehydes with simple dienes

A highly regioselective and diastereoselective oxa-Diels-Alder reaction catalyzed by AlCl3 has been developed. This reaction is efficient and characterized by good functional group compatibility, F, Cl, CN, NO2, OMe and thiophenyl groups are tolerated. A Lewis acid catalyzed concerted cycloaddition mechanism is proposed based on the results.

A New Approach to Non-Coordinating Anions: Lewis Acid Enhancement of Porphyrin Metal Centers in a Zwitterionic Metal-Organic Framework

We describe a new strategy to generate non-coordinating anions using zwitterionic metal-organic frameworks (MOFs). By assembly of anionic inorganic secondary building blocks (SBUs) ([In(CO2)4]-) with cationic metalloporphyrin-based organic linkers, we prepared zwitterionic MOFs in which the complete internal charge separation effectively prevents the potential binding of the counteranion to the cationic metal center. We demonstrate the enhanced Lewis acidity of MnIII- and FeIII-porphyrins in the zwitterionic MOFs in three representative electrocyclization reactions: [2 + 1] cycloisomerization of enynes, [3 + 2] cycloaddition of aziridines and alkenes, and [4 + 2] hetero-Diels-Alder cycloaddition of aldehydes with dienes. This work paves a new way to design functional MOFs for tunable chemical catalysis.

Nanoporous iron(III) porphyrin frameworks: an efficient catalyst for [4+2] cycloaddition reactions of unactivated aldehydes with a diene

The one pot conversion of several unactivated aldehydes with a diene to their corresponding [4+2] cycloaddition products has been studied using newly synthesized nanoporous iron(iii) porphyrin frameworks as catalysts. The heterogeneous catalysts have been synthesized from 5,10,15,20-tetrakis(4-cyanophenyl)porphyrinato iron(iii) chloride (PFe·X) with the help of Pinnar type synthesis. The catalytic activity of the monomeric catalyst (PFe·X) vs. that of the new nanoporous catalysts (1·X) where X = Cl-, BF4-etc. in the reaction of dienes and aldehydes were then compared. The structure of the catalysts was investigated using different characterization techniques including Fourier transform infrared spectroscopy (FT-IR), CHN, atomic absorption spectroscopy (AAS), scanning electron microscopy (SEM) and the BET surface area which was measured via a physisorption study of N2 at 77 K. The reaction parameters determining yield, including the quantity of the catalyst and the solvent, were optimized to afford the hetero Diels-Alder product efficiently. It was observed that the nanoporous catalysts (1·X) were much superior to the monomeric (PFe·X) catalysts at giving selective products in high yields. Secondly, the new catalysts remained active for at least 8 cycles without any observable decay in their catalytic ability. Attempts are made to rationalize the results by considering the nature of X and the BET surface area of the 1·X catalysts.

Metalloporphyrin-Based Hypercrosslinked Polymers Catalyze Hetero-Diels–Alder Reactions of Unactivated Aldehydes with Simple Dienes: A Fascinating Strategy for the Construction of Heterogeneous Catalysts

We describe a novel and intriguing strategy for the construction of efficient heterogeneous catalysts by hypercrosslinking catalyst molecules in a one-pot Friedel–Crafts alkylation reaction. The new hypercrosslinked polymers (HCPs) as porous solid catalysts exhibit the combined advantages of homogeneous and heterogeneous catalysis, owing to their high surface area, good stability, and tailoring of catalytic centers on the frameworks. Indeed, a new class of metalloporphyrin-based HCPs were successfully synthesized using modified iron(III) porphyrin complexes as building blocks, and the resulting networks were found to be excellent recyclable heterogeneous catalysts for the hetero-Diels–Alder reaction of unactivated aldehydes with 1,3-dienes. Moreover, this new strategy showed wide adaptability, and many kinds of homogeneous-like solid-based catalysts with high catalytic performance and excellent recyclability were also constructed.

Silver Tetrafluoroborate-Catalyzed Oxa-Diels-Alder Reaction between Electrically Neutral Dienes and Aldehydes

Chemoselective oxa-Diels-Alder reactions between electrically neutral 1,3-dienes and various aldehydes were achieved using the commercially available silver tetrafluoroborate (AgBF4) as catalyst. This catalytic process has high functional group tolerance. Heteroatoms at the β-position of the aryl aldehydes can greatly promote the reactivity of the substrates even with heterocyclic aldehydes that were previously believed to be unreactive for the oxa-Diels-Alder reaction. In addition, acroleins with β-heteroatom substitution are also good substrates. High chemoselectivity and regioselectivity were achieved at room temperature for the oxa-Diels-Alder reaction between acroleins and stoichiometric simple 1,3-dienes.

Carbocation Catalysis: Oxa-Diels-Alder Reactions of Unactivated Aldehydes and Simple Dienes

The versatility of the trityl cation (TrBF4) as a highly efficient Lewis acid organocatalyst is demonstrated in the oxa-Diels-Alder reaction of various unactivated aromatic and aliphatic aldehydes and simple unactivated dienes, such as isoprene and 2,3-dimethylbutadiene. The transformation proceeds smoothly to give 3,6-dihydropyrane adducts in high to moderate yields with catalyst loadings down to 1.0 mol-% under mild reaction conditions. In contrast to most previously reported strategies, this protocol does not require substrate functional group activation, neither by electron-deficient aldehydes (2-oxo aldehydes) or electron-rich dienes (methoxy or amino-butadiene).

A highly stable porphyrinic zirconium metal-organic framework with shp-a topology

Through a kinetically controlled synthetic process, we synthesized PCN-223, a new porphyrinic Zr-MOF constructed from the newly reported hexagonal prismatic 12-connected Zr6 cluster through an unusual disordered arrangement, giving rise to the first example of the shp-a network in MOFs. With its extremely high connectivity, PCN-223 shows high stability in aqueous solutions with a wide range of pH. Cationic PCN-223(Fe) formed by postsynthetic treatment is an excellent recyclable heterogeneous catalyst for the hetero-Diels-Alder reaction.

Cationic iron(III) porphyrin-catalyzed [4 + 2] cycloaddition of unactivated aldehydes with simple dienes

Cationic iron(III) porphyrin was found to be an efficient catalyst for the highly chemoselective hetero-Diels-Alder-type reaction of aldehydes with 1,3-dienes. The catalyzed process did not require the use of electron-deficient aldehydes such as glyoxylic acid derivatives or activated electron-rich 1,3-dienes such as Danishefsky's diene and Rawal's diene. The high functional group tolerance and robustness of the catalyst were demonstrated. Further, the potential utility of the catalyst was demonstrated by performing the cycloaddition in the presence of water and by carrying out cycloaddition of an unactivated ketone such as cyclohexanone with a diene.