Prins Reaction Research Articles

MoO3-MCM-41 materials as effective catalysts in Prins reaction of isoprenol with butanal followed by esterification in one-pot reaction arrangement

MoO3-MCM-41 materials as effective catalysts in Prins reaction of isoprenol with butanal followed by esterification in one-pot reaction arrangement

Tracking the coupling conversion of C1-C4 aldehydes with methanol-to-hydrocarbon reaction

Small-molecule aldehydes are promising additives to regulate product distribution in methanol-to-hydrocarbon (MTH) reaction. Herein, the co-feeding of C1-C4 aldehydes with methanol resulted in a significant increase in aromatic formation with the order: acetaldehyde > formaldehyde > propanal ≈ butanal. The mechanistic basis for this enhancement in aromatic production derived from both a direct participation pathway of aldehydes and an indirect pathway via driving the aromatic-based cycle. C2+ aldehydes could undergo multiple aldol-condensation on Brønsted acid sites to form larger alkenals, followed by sequential cyclization-dehydration reaction to cycloalkenes or aromatic species. The Prins reaction could be extended to all C1-C4 aldehydes with alkenes by generating the corresponding dienes. The hydrogen transfer from methanol to C2+ aldehydes produced C2+ olefins and formaldehyde, which would lead to extra formaldehyde-mediated aromatic formation pathway. The intricate evolution pathway of C1-C4 aldehydes in MTH reaction was constructed by detecting abundant oxygenate and hydrocarbon intermediates.

Synthesis of 3-methyl-3-buten-1-ol by supercritical CO2 in coordination with HZSM-5-catalyzed formaldehyde-isobutene Prins reaction.

The reaction solvent and catalyst play essential roles in the Prins reaction for the synthesis of 3-methyl-3-buten-1-ol (MBO) from formaldehyde and isobutene. The reactivity of the solid base-catalyzed Prins condensation reaction by formaldehyde and isobutene in supercritical CO2 was investigated using CsH2PO4-modified HZSM-5. We found that the alkaline sites of the alkali-loaded catalyst could extract the α-H on isobutene to generate olefin carbon-negative ions, while the supercritical CO2 with weak Lewis acidity could activate formaldehyde to carbon-positive ions, which can combine more easily with carbon-negative isobutene to react, thus improving the reactivity of the reaction system.

Hydroxymethylation hydroxylation of 1,3-diarylpropene through a catalytic diastereoselective Prins reaction: cyclization logic and access to brazilin core

A catalytic diastereoselective Prins reaction for hydroxymethylation and hydroxylation of 1,3-diarylpropene was successfully utilized to prepare various 1,3-dioxanes 7 in 14–88% yields. Take advantage of the synthetic intermediate 7h, the key B/C rings in brazilin core could be constructed by the sequential of Friedel–Crafts/Ullmann-Ma rather than Ullmann-Ma/Friedel–Crafts reactions.Graphical

Advances in the Study of the Prins Reaction and the Prins Cyclization Reaction

Advances in the Study of the Prins Reaction and the Prins Cyclization Reaction

Acidic ionic liquid-functionalized ordered mesoporous polymers: Highly efficient solid acid catalysts for water-medium organic reactions

Strong acidic ionic liquid-functionalized mesoporous organic material (MPOM-T-AIL) has been created by quaternary ammonization of mesoporous organic material (MPOM) with 1,3-propane sultone and subsequent strong acid (H2SO4 or HSO3CF3) acidification. The novel supporting material, MPOM, had high nitrogen content and was synthesized by direct high-temperature (400–550 °C) polymerization of an easily prepared and low cost protic salt [pPDA][2HSO4], which was obtained by simple neutralization of p-phenylenediamine with two equivalents of H2SO4. MPOM-T-AIL possesses high BET specific surface area, ordered and uniform mesoporosity, hydrophobic property, and highly active acidic ionic liquid components. Catalytic tests in the water-medium Prins reactions and acetalization of benzaldehyde with ethylene glycol showed that MPOM-T-AIL exhibits much better catalytic activities and reusabilities than commercially available solid acid catalysts Amberlyst 15 and H-ZSM-5, and mineral acid H2SO4. Additionally, MPOM-T-AIL significantly improved the catalytic selectivity of the water-medium Prins reaction, which was strongly related to its hydrophobic property. MPOM-T-AIL with excellent catalytic performance is a promising new solid acid catalyst for various acid-catalyzed reactions.

Highly Effective and Broad-Spectrum Antimicrobial Quaternary Ammonium Salts Containing Camphene Structure: Preparation, Surface-Active Properties, and Bioassay.

A series of novel quaternary ammonium salts (QASs) (4a-4n) comprising a camphene moiety were synthesized for the first time. Fourteen examples were prepared from camphene through Prins reaction, halogenation, and quaternarization, successively. The structures of the synthesized QASs were analyzed by Fourier transform infrared spectroscopy, 1H NMR, 13C NMR and high-resolution mass spectrometry. Surface-active properties, emulsifying abilities, and foaming properties of the investigated compounds were then studied. The antimicrobial activities of these QASs against Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis), Gram-negative bacteria (Escherichia coli and Klebsiella pneumoniae), and fungi species (Candida albicans, Candida tropicalis, and Aspergillus niger) were determined by the microdilution method. The results showed that the chemical structural factors, including types of substitutes and alkyl chain length, might be correlated with the lipid-water partition coefficient (cLog P), which played a critical role in the antimicrobial process. Compounds with alkyl chain lengths (N) in the range of 10-14 were relatively more active, while compounds bearing pyridinium, benzyl, methylimidazolium groups, or varied alkyl chain lengths (N < 5 and N > 16) were almost inactive. Compound 4k possessing a dodecyl group exhibited the most effective and broad-spectrum antimicrobial activity against almost all tested bacteria and fungi with the minimal inhibitory concentration values ranging from 0.24 to 0.98 μg/mL.

A Brief Review on Proved Approaches for the Formation of Oxygen Containing Heterocyclic Compounds through a Tandem Prins Cyclization

: Prins reaction is a very useful and important reaction in the field of synthetic organic chemistry. Prins cyclization is one of the greatest significant synthetic approaches in the total synthesis of various natural compounds especially pyran and furan units. The addition of aldehydes to olefinic compounds utilizing acid catalyst has become important for the industry. : Aldehydes and alkenes to give different products depending on the reaction conditions, yield an acidcatalyzed reaction. Formation of Carbon-Carbon bonds is useful to produce 1,3-diol, 1,3-dioxane, β- halohydrin and allylic alcohols and tetrahydropyrans by using this methodology. Now coming to the point of tandem Prins cyclization, this method is very useful for the synthesis of fused compounds and also for the construction of spirocyclic compounds such as tetrahydropyrans or furans. The present brief review mainly deals with the development of the synthesis of oxygen-containing heterocyclic compounds by using prins/tandem prins cyclization. This current review is focused mainly on tandem prins cyclization’s reactions for the particular recent applications and what methods are used for the construction of the oxygen contained heterocyclic compounds.

Acid site requirement and reaction pathway for selective bio-butadiene synthesis by 1,3-butanediol dehydration

Gas phase dehydration of 1,3-butanediol was studied at 523 K on solid catalysts with different acidic and physicochemical properties: Al2O3, SiO2/Al2O3, NaZSM5, HZSM5 and TPA (tungstophosphoric acid)/SiO2. The solids were characterized by N2 physisorption, DRX and FTIR spectroscopy of pyridine. The main products were butadiene and 3-buten-1-ol via dehydration route, in addition to propene plus formaldehyde and 4-methyl-1,3-dioxane by reverse or direct Prins condensation, respectively. The effect of reaction temperature (473–573 K) on 1,3-butanediol conversion and products distribution was evaluated. The relationship between the nature of catalytic sites and the main reaction pathway was analyzed. Catalysts with Brønsted acid sites promoted the dehydration reaching the highest yield of butadiene (75 %) on TPA/SiO2 while Lewis acid sites favored the inverse Prins reaction route to propene and formaldehyde. Further studies using the possible intermediates of 1,3-butanediol dehydration were performed and probable mechanisms of formation of the different products were proposed.

Total synthesis of a putative yuzurimine-type Daphniphyllum alkaloid C14‑epi-deoxycalyciphylline H

One of the largest subfamilies within the famous Daphniphyllum alkaloid family is made up of the yuzurimine-type (or macrodaphniphyllamine-type) alkaloids. Their complex aza-polycyclic caged structures, several contiguous stereogenic centers, and vicinal all-carbon quaternary centers make these alkaloids formidable challenge for synthetic chemists. Recently, synthesis of these alkaloids has received extensive attention from our community. Herein, we wish to report the total synthesis of C14‑epi-deoxycalyciphylline H, a putative member of yuzurimine-type alkaloid subfamily. Key transformations employed in our approach include an intramolecular Prins reaction and a Pd-catalyzed enyne cycloisomerization. In addition, synthesis of a daphnezomine L-type alkaloid, paxdaphnidine A, was also studied.

Acid treated montmorillonite - efficient catalyst in Prins reaction of alpha-methylstyrene with paraldehyde

Acid treated montmorillonite was used as a catalyst in Prins reaction of α methylstyrene with paraldehyde giving 2,4,6-trimethyl-4-phenyl-1,3-dioxane (Vertacetal). The product of this reaction is a bioactive compound, which can interact with GABA (gamma-aminobutyric acid) receptors and has fragrant properties. Montmorillonite (used for this reaction as catalyst) was prepared by treatment with hydrochloric, nitric, sulfuric or chloroacetic acid. The influence of acid used for treatment, and other reaction conditions (reaction temperature, solvent, reactant molar ratio, catalyst amount) on the reaction course were tested. Acid treated montmorillonite proved to be a catalyst suitable for this reaction – a high yield of desired product was obtained (>94%) at room temperature using different solvents. Solvent choice showed to be crucial for the reaction – the best results were obtained using nitromethane or 1,4-dioxane. The catalyst can be reused one time after calcination at 300 °C.

Recent Advances in the Prins Reaction.

The Prins reaction is a very convenient synthetic platform for the preparation of oxygen-containing heterocyclic compounds, especially tetrahydropyrans and tetrahydrofurans. While this reaction has been extensively used by synthetic chemists since its discovery, the last years have witnessed impressive improvements in its performance and scope and especially in the development of new catalytic and enantioselective versions. This mini-review presents these recent advances through selected representative examples.

Synthesis of Heterocyclic Scaffolds via Prins, Oxonium-Ene and Related Cyclization Reactions

AbstractA variety of oxygen, nitrogen and sulfur heterocyclic compounds are synthesized via one-pot multicomponent Prins, aza-Prins, thia-Prins, oxonium-ene, iminium-ene and thionium-ene cyclization reactions. The reactions proceeds with high diastereo- and regioselectivity. Importantly, C–C, C–N, C–O and C–S bonds are formed in a singsle step. These procedures are extended for the synthesis of biologically active molecules and natural products.1 Introduction2 Prins Cyclization Reactions3 Oxonium-Ene Cyclization Reactions4 Conclusion

Synthesis of Spiro[furan-2,1'-isoindolin]-3'-ones from 2-(4-Hydroxybut-1-yn-1-yl)benzonitriles and Aryl Aldehydes under the Action of Triflic Acid.

The synthesis of spiro[furan-2,1'-isoindolin]-3'-ones from 2-(4-hydroxybut-1-yn-1-yl)benzonitriles and aryl aldehydes is demonstrated. It involves the initial formation of dihydrofuranylideneisoindolinone via intramolecular sequential Prins and Ritter reactions, followed by the ring opening of the furanyl moiety to generate N-acyliminium ions and alcohols for the final cyclization reaction, and the spiro-cyclic compounds are produced in moderate to good yields. It is a one-pot, three-component reaction in which one new quaternary carbon, two five-membered rings, one C-N bond, two C-O bonds, and one C-C bond are formed. The reaction is carried out with a Brønsted acid from 0 °C to room temperature within a short period of time.

Kinetics of the Reaction of 2-Methylpropene with Formaldehyde in the Presence of Synthetic Zeolites

It is well known that zeolites exhibit catalytic activity in the Prins reaction. It was found that their use makes it possible to increase the selectivity of the Prins reaction with 2-methylpropene, and the dependences of the effective rate constants of the consumption of formaldehyde and the accumulation of 4,4‑dimethyl-1,3-dioxane on the pore diameter of zeolites are extremal. This work is relevant because the knowledge of the kinetics of the Prins reaction in the presence of type A and X zeolites can contribute to the regulation of selectivity for the formation of oxygen-containing compounds, in particular, industrially valuable 4,4-dimethyl-1,3-dioxane upon the interaction of formaldehyde and 2-methylpropene.

Access to Hexahydroindeno[2,1-c]pyran-Based Propellanes by a Domino Prins/Friedel–Crafts Cyclization

AbstractStarting from readily available cyclic homoallylic alcohols, a Prins reaction allowed the formation of a bicyclic tetrahydropyranyl carbocation intermediate that is only trapped by electron-rich aromatic rings according a further intramolecular Friedel–Crafts reaction leading to new [4.4.3]propellane structures.

Bioinspired Total Synthesis of Erectones A and B, and the Revised Structure of Hyperelodione D

AbstractThe field of biomimetic synthesis seeks to apply biosynthetic hypotheses to the efficient construction of complex natural products. This approach can also guide the revision of incorrectly assigned structures. Herein, we describe the evolution of a concise total synthesis and structural reassignment of hyperelodione D, a tetracyclic meroterpenoid derived from a Hypericum plant, alongside some biogenetically related natural products, erectones A and B. The key step in the synthesis of hyperelodione D forms six stereocentres and three rings in a bioinspired cascade reaction that features an intermolecular Diels–Alder reaction, an intramolecular Prins reaction and a terminating cycloetherification.

Bioinspired Total Synthesis of Erectones A and B, and the Revised Structure of Hyperelodione D.

The field of biomimetic synthesis seeks to apply biosynthetic hypotheses to the efficient construction of complex natural products. This approach can also guide the revision of incorrectly assigned structures. Herein, we describe the evolution of a concise total synthesis and structural reassignment of hyperelodione D, a tetracyclic meroterpenoid derived from a Hypericum plant, alongside some biogenetically related natural products, erectones A and B. The key step in the synthesis of hyperelodione D forms six stereocentres and three rings in a bioinspired cascade reaction that features an intermolecular Diels–Alder reaction, an intramolecular Prins reaction and a terminating cycloetherification.

The Catalytic Asymmetric Intermolecular Prins Reaction.

Despite their significant potential, catalytic asymmetric reactions of olefins with formaldehyde are rare and metal-free approaches have not been previously disclosed. Here we describe an enantioselective intermolecular Prins reaction of styrenes and paraformaldehyde to form 1,3-dioxanes, using confined imino-imidodiphosphate (iIDP) Brønsted acid catalysts. Isotope labeling experiments and computations suggest a concerted, highly asynchronous addition of an acid-activated formaldehyde oligomer to the olefin. The enantioenriched 1,3-dioxanes can be transformed into the corresponding optically active 1,3-diols, which are valuable synthetic building blocks.

Deactivation of Zeolite Catalysts in the Prins Reaction between Propene and Formaldehyde in the Liquid Phase

The Prins reaction between propene and formaldehyde was studied over H-BEA, H-FAU, H-MFI and H-MOR zeolites at 150 °C in liquid phase. It was found that the H-BEA sample is the most active and selective toward buta-1,3-diene; the H-MFI is a potential catalyst for 3-buten-1-ol synthesis, while H-FAU can be used for 4-methyl-1,3-dioxane production. It had been confirmed that zeolite textural and acidic properties influence catalyst behaviour: the acidic properties influence sample activity, while product distribution is controlled by pore volume and effective pore diameter. The sample’s deactivation process had been studied and the kinetic model of deactivation was proposed. It was shown that the deactivation rate for the H-MFI catalyst is four times greater than for the H-BEA catalyst, probably because its strong/weak acid sites ratio is much more high than for the H-BEA.