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Upstream product

• 1122-03-8 4,4,5-trimethyl-1,3-dioxane 
• 100-52-7 benzaldehyde 
• 513-81-5 2,3-dimethyl-buta-1,3-diene 
• 23092-23-1 3-methyl-1-phenylbut-3-en-1-ol 

Relevant academic research and scientific papers

C-C bond formation via 1,2-addition of a tert-butylzinc reagent and carbonyls across conjugated dienes

A mixture of t-butylzinc halide and an aldehyde reacts with conjugated dienes to provide 2-neopentyl homoallyl alcohols in high yields by 1,2-addition. Without the aldehyde, under carbon dioxide atmospheric pressure, the three components of t-butylzinc ha

Ligand-Directed Conformational Control over Porphyrinic Zirconium Metal-Organic Frameworks for Size-Selective Catalysis

Zirconium-based metal-organic frameworks (Zr-MOFs) have aroused enormous interest owing to their superior stability, flexible structures, and intriguing functions. Precise control over their crystalline structures, including topological structures, porosity, composition, and conformation, constitutes an important challenge to realize the tailor-made functionalization. In this work, we developed a new Zr-MOF (PCN-625) with a csq topological net, which is similar to that of the well-known PCN-222 and NU-1000. However, the significant difference lies in the conformation of porphyrin rings, which are vertical to the pore surfaces rather than in parallel. The resulting PCN-625 exhibits two types of one-dimensional channels with concrete diameters of 2.03 and 0.43 nm. Furthermore, the vertical porphyrins together with shrunken pore sizes could limit the accessibility of substrates to active centers in the framework. On the basis of the structural characteristics, PCN-625(Fe) can be utilized as an efficient heterogeneous catalyst for the size-selective [4 + 2] hetero-Diels-Alder cycloaddition reaction. Due to its high chemical stability, this catalyst can be repeatedly used over six times. This work demonstrates that Zr-MOFs can serve as tailor-made scaffolds with enhanced flexibility for target-oriented functions.

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

Selective Activation of Aromatic Aldehydes Promoted by Dispersion Interactions: Steric and Electronic Factors of a π-Pocket within Cage-Shaped Borates for Molecular Recognition

Selective bond formations are one of the most important reactions in organic synthesis. In the Lewis acid mediated electrophile reactions of carbonyls, the selective formation of a carbonyl–acid complex plays a critical role in determining selectivity, wh

Ruthenium Metathesis: A Key Step to Access a New Cyclic Tetrasubstituted Olefin Platform

An rapid and mild synthetic route for the preparation of cyclic tetrasubstituted platforms via ruthenium-catalyzed ring-closing metathesis (RCM) has been developed. This process tolerates a wide range of functionalities such as nitrogen, oxygen, sulfur, silicon, and carbon tethered groups, as well as very challenging fluorine and boron atoms (36 derivatives, up to 96%). This diversity-oriented method was further demonstrated by the postfunctionalization reactions, such as Pd-couplings, N-substitution, and reductive amination introducing a morpholine moiety.

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

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.

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.

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.

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.