Polycyclic Compounds Research Articles

Synthesis and Structural and Optical Behavior of Dehydrohelicene-Containing Polycyclic Compounds.

Dehydrohelicene-based molecules stand out as highly promising scaffolds and captivating chiroptical materials, characterized by their unique chirality. Their quasi-helical π-conjugated molecular architecture, featuring successively ortho-annulated aromatic rings, endows them with remarkable thermal stability and optical properties. Over the past decade, diverse approaches have emerged for synthesizing these scaffolds, reinvigorating this field, with anticipated increased attention in the coming years. This review provides a comprehensive overview of the historical evolution of dehydrohelicene chemistry since the pioneering work of Zander and Franke in 1969 and highlights recent advancements in the synthesis of various molecules incorporating dehydrohelicene motifs. We elucidate the intriguing structural features and optical merits of these molecules, occasionally drawing comparisons with their helicene or circulene analogs to underscore the significance of the bond between the helical termini.

1,3-Bishomocubane: a kinetic rock, a thermodynamic powerhouse and a compelling chiral synthetic scaffold.

Over the last several decades, saturated polycyclic cage compounds have remained a point of interest for organic chemists because of their unique characteristics and reactivity. For the first time, a detailed analysis of the synthesis, properties and transformations of 1,3-bishomocubanes, which fall under the rare category of chiral cage compounds, is provided in this article. This review which also includes the authors' work in this area over the last decade is expected to serve as a valuable resource for chemists interested in the fascinating chemistry and properties of polycyclic cage compounds.

A visible-light-induced cascade cyclization strategy for the synthesis of N,S-containing polycyclic compounds

A selective synthesis of nonsymmetrical polyheterocycles via visible-light-induced cyclization of functionalized 1,3-diynes and disulfide has been established.

Direct C-H electrophilic borylation with (C6F5)2B-NTf2 to generate B-N dibenzo[a,h]pyrenes.

The borylation of aryl substituted pyridines is an effective way of preparing B-N doped conjugated organic frameworks. Trihaloborane Lewis acids are often employed for this protocol, and may require further functionalization to replace the remaining halides on boron. We report a new, fully characterized, electrophilic borylating agent, (C6F5)2B(κ2-NTf2), that smoothly incorporates a -B(C6F5)2 unit into the model substrate 2-phenylpyridine. To demonstrate its utility in preparing more complex B-N doped structures, we use it to prepare seven examples of the 6a,13a-diaza-7,14-dibora-dibenzo[a,h]pyrene framework, with substituents of varying donor properties. The structural, redox, and photophysical properties of this new family of B-N doped polycyclic hydrocarbon compounds were probed experimentally and computationally.

Tetraasteranes as homologues of cubanes: effective scaffolds for drug discovery.

Classical hydrocarbon scaffolds have long assisted in bringing new molecules to the market for a variety of applications, but one notable omission is that of tetraasteranes, which are homologues of cubanes belonging to a class of polycyclic hydrocarbon cage compounds. Tetraasteranes exhibit potential as scaffolds in drug discovery due to their identical cyclobutane structures and rigid conformation resembling cubanes. Based on the studies of the physical and chemical properties of tetraasteranes by density functional theory, three series of compounds were designed as homologues of cubanes by the substitution of cubane scaffolds in pharmaceuticals with tetraasteranes. Their potential for pharmaceutical applications was evaluated in silico by molecular docking and dynamics simulations. Their pharmacokinetic and physicochemical properties were studied by the ADMET (absorption, distribution, metabolism, excretion, and toxicity) analysis. The results indicate that tetraasteranes may be scaffolds as novel bioisosteres of cubanes, as well as hydrogen bond donors or acceptors, which enhance the affinity between ligands and receptors with more stable binding behavior and feasible tolerability in ADMET. All these findings provide new opportunities for tetraasteranes to serve as effective pharmaceutical scaffolds for drug discovery and to accelerate the drug discovery process by repurposing both new and old commercial compounds.

Copper-catalysed perarylation of cyclopentadiene: synthesis of hexaarylcyclopentadienes.

While hexaphenylsilacyclopentadiene (hexaphenylsilole) is viewed as an archetypal Aggregation-Induced Emission (AIE) luminogen, its isostructural hydrocarbon surrogate hexaphenylcyclopentadiene has strikingly never been investigated in this context, most probably due to a lack of synthetic availability. Herein, we report a straightforward synthesis of hexaphenylcyclopentadiene, via the direct perarylation of cyclopentadiene upon copper(i) catalysis under microwave activation, with the formation of six new C-C bonds in a single synthetic operation. Using zirconocene dichloride as a convenient source of cyclopentadiene and a variety of aryl iodides as coupling partners, this copper-catalysed cross-coupling reaction gave rise to a series of unprecedented hexaarylcyclopentadienes. The latter are direct precursors of extended π-conjugated polycyclic compounds, and their cyclodehydrogenation under Scholl reaction conditions yielded helicenic 17,17-diarylcyclopenta[l,l']diphenanthrenes. These structurally complex polyannelated fluorene derivatives can now be prepared in only two synthetic steps from cyclopentadiene.

Visible light-driven dearomative ring expansion of (aza)arenes to access dihydrofuran-based polycyclic compounds.

The dearomative expansion of aromatic rings has long been pursued by chemists due to its potential to provide tractable approaches for synthesizing valuable non-aromatic molecules. To circumvent the conventional use of hazardous and unstable diazo compounds, photochemical synthesis has recently emerged as a promising platform. However, protocols that can effectively handle both arenes and azaarenes remain scarce. Herein, we introduce a generic strategy that efficiently converts β-(aza)aryl-β-substituted enones into biologically significant cycloheptatriene derivatives, including their aza-variants. This method allows for the easy modulation of diverse functional groups on the product and demonstrates a wide substrate scope, evidenced by its excellent tolerance to various drug motifs and good compatibility with five-membered azaarenes undergoing ring expansion. Moreover, DFT calculations of plausible mechanisms have motivated the implementation of an important cascade diradical recombination strategy for 1,3-dienones, thus facilitating the synthesis of valuable 2-oxabicyclo[3.1.0]hex-3-ene derivatives.

Iodomethane in C1 chemistry: application in palladium-catalyzed [2 + 2 + 1] annulation.

An efficient palladium-catalyzed [2 + 2 + 1] annulation of 3-iodochromones, bridged olefins, and iodomethane is described, affording a range of chromone-containing polycyclic compounds. Additionally, the corresponding deuterated products were smoothly obtained with iodomethane-d3 instead of iodomethane. Moreover, the synthetic utility of this method is further substantiated by gram scale preparation and application to late-stage modification of estrone.

Regioselective synthesis of N-containing polycyclic compounds via radical annulation cyclization of 1,7-dienes with aldehydes.

A convenient method for oxidant-promoted radical cascade acylation or decarbonylative alkylation of 1,7-dienes with aldehydes has been established. This method allows for the rapid construction of N-containing polycyclic skeletons in a highly regio- and stereoselective manner. This transformation provides a simple and efficient method for the preparation of a range of tetrahydro-6H-indeno[2,1-c]quinolinone derivatives by sequential formation of three new carbon-carbon bonds. Additionally, this radical cascade cyclization can selectively convert aldehydes into aroyl/primary aliphatic acyl radicals and secondary or tertiary alkyl radicals.

Accessing pyrrolo[1,2-a]indole derivatives via visible-light-induced dearomatizative cyclization of indoles.

Pyrrolo[1,2-a]indoles are structurally important scaffolds in many natural products and bioactive compounds. Herein, we report a novel synthetic method for pyrrolo[1,2-a]indole derivatives through visible-light-induced cascade dearomatizative cyclization of indoles with external nucleophiles. Moderate yields, good diastereoselectivities, and excellent regioselectivities were generally observed with the resultant indole-fused polycyclic compounds.

Photoredox- and piezo-catalysed access to complex trifluoromethylated polycyclic structures from ynamides

Under photoredox- and piezo-catalysis conditions, ynamides undergo a radical to yield polycyclic compounds by fully utilizing the ynamide unsaturations.

New strategies for asymmetric photocatalysis: asymmetric organocatalytic/photoredox relay catalysis for efficient synthesis of polycyclic compounds containing vicinal amino alcohols

New strategies for asymmetric photocatalysis: asymmetric organocatalytic/photoredox relay catalysis for efficient synthesis of polycyclic compounds containing vicinal amino alcohols

Crude Saponins from Chenopodium quinoa Willd. Reduce Fusarium Wilt Infection in Tomato Seedlings

Quinoa saponins are pentacyclic triterpene compounds composed of one triterpenoid glycoside and two different sugar chains. Previous studies have showed that natural quinoa saponins showed little or no antifungal activity, and there are few reports about their antifungal effects in recent decades. Fusarium wilt caused by Fusarium oxysporum f. sp. lycopersici (FOL) is the most serious for tomatoes in the field and under greenhouse conditions. The main objective of this study was to investigate the effectiveness of different concentrations and application modes of crude saponins from quinoa bran against the causal pathogen of tomato wilt under a greenhouse experiment. The results showed that the anti-FOL activity of quinoa saponins was weak in vitro, but significantly enhanced in vivo. Tomato seeds and seedlings treated with solution of quinoa saponins at 0.5 and 1.0 g/L significantly reduced the disease incidence (%) of tomato Fusarium wilt. The treatment types of saponin solution have influence on the preventive effects (%) of tomato seedlings against Fusarium wilt, among them, root soaking > foliar spray > seed soaking. The treatment of seed soaking with quinoa saponins inhibited germination of tomato seeds to some extent. However, the germination rate of tomato seeds after saponin soaking was comparable to the chemical pesticide (thiram carboxin); therefore, it could be used to control tomato wilt disease. This is due to the fact that the antifungal activity of quinoa saponins in vivo was much higher than that in vitro when the saponin concentration was between 0.5–1.0 g/L, indicating that the antifungal activity of quinoa saponins may be achieved mainly by inducing resistance. This investigation supports the potential use of quinoa saponins as a supplier of antifungal compounds, and could be the foundation for a future study examining the use of quinoa bran as a new resource against FOL.

Heavy Tetrel Clusters Based on the Bicyclobutane Framework: Bicyclo[1.1.0]butanes, [1.1.1]Propellanes, and Tricyclo[2.1.0.02,5 ]pentanes.

In this review, the current state of affairs in the novel field of the group 14 element clusters based on the bicyclo[1.1.0]butane framework, namely, bicyclo[1.1.0]butane, [1.1.1]propellane, and tricyclo[2.1.0.02,5 ]pentane derivatives, are overviewed. Structural similarities and differences between these three classes of highly strained polycyclic compounds are considered from the viewpoint of the critically important nature of their bridgehead bonds. Synthetic strategies towards bicyclo[1.1.0]butanes, [1.1.1]propellanes, and tricyclo[2.1.0.02,5 ]pentanes, as well as their peculiar structural and bonding features, and specific reactivity, are also presented and discussed in this review.

Enantioselective and Regiodivergent Synthesis of Dihydro-1,2-oxazines from Triene-Carbamates via Chiral Phosphoric Acid-Catalysis.

Conjugated trienes are fascinating building blocks for the rapid construction of complex polycyclic compounds. However, limited success has been achieved due to the challenging regioselectivity control. Herein, we report an enantio- and diastereoselective process allowing to regioselectively control the functionalization of NH-triene-carbamates. Synthesis of chiral cis-3,6-dihydro-2H-1,2-oxazines is achieved by a chiral phosphoric acid catalyzed Nitroso-Diels-Alder cycloaddition involving [(1E,3E,5E)-hexa-1,3,5-trien-1-yl]carbamates. Moreover, modular access to three different regioisomers with excellent diastereoselectivities and high to excellent enantioselectivities is obtained by a careful choice of the reaction conditions. A computational study reveals that the regioselectivity is influenced by the steric demand of the substituents at the 6-position of the triene, as well as noncovalent interactions between the two cycloaddition partners. Utility of each regioisomeric cycloadduct is highlighted by a variety of synthetic transformations.

A Research on Futuristic Magical effect of Oleanolic Acid

Oleanolic acid (3β-hydroxyolean-12-en-28-oic acid) is a pentacyclic triterpenoid compound and its derivatives possess several promising pharmacological activities. Here, we aimed to investigate the antioxidant and free radical scavenging properties of ethanolic extracts of Oleanolic acid from Ocimum sanctum. antioxidants entrapped in nanogel or hollow particles, used to provide better stability, gradual and sustained release, biocompatibility, and targeted delivery of the antioxidants with superior antioxidant profiles. The antioxidant activities were assessed using 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging and superoxide radical scavenging assays.

2α, 3α, 24-Thrihydroxyurs-12-en-24-ursolic acid enhances the cytotoxic effect of cisplatin on oral cancer cells by down-regulating autophagy.

This study aimed to investigate the effect and mechanism of 2α, 3α, 24-thrihydroxyurs-12-en-24-ursolic acid (TEOA) alone or in combination with cisplatin on oral cancer. TEOA, a pentacyclic triterpenoid compound isolated from the roots of Actinidia eriantha, has demonstrated antitumor activity in preclinical experiments. However, its role in oral cancer remains poorly understood. Our findings revealed that a low concentration of TEOA did not exhibit significant cytotoxicity against oral squamous cell carcinoma cells. However, when combined with cisplatin, TEOA showed a significant therapeutic effect. The combined treatments resulted in a significant inhibition of proliferation and migration and a significant increase in apoptosis of squamous cell carcinoma cells. Cisplatin exposure increased autophagy levels, which may contribute to chemoresistance. Of note, the presence of TEOA significantly inhibited cisplatin-induced autophagy, leading to improved chemotherapy efficacy. Our findings indicate that a mild low dosage of TEOA may enhance the cytotoxic effect of cisplatin by downregulating autophagy in oral cancer cells.

B(C6 F5 )3 -Catalyzed [2+3]-Cyclative o,m-diC-H Functionalization of Phenols.

Metal-free catalytic C-H functionalization is highly desired for the construction of C-C bonds. We herein report a highly chemoselective consecutive C-H [2+3]-cyclative functionalization for the simultaneous formation of two C-C bonds with construction of polycyclic phenols catalyzed by commercially available and low-cost B(C6 F5 )3 . This catalytic system tolerates a wide range of substrate scope, providing a series of 2,6,7,8-tetrahydroacenaphthylen-3-ol-type polycyclic compounds efficiently. Several derivatizations of the catalytic products have also been conducted to show the potential application of this method in synthesis of polycyclic compounds.

Synthesis of 10-Membered Azecines through Pd-Catalyzed Formal [6+4] Cycloaddition and Their Transannular Reaction to Polycyclic Compounds.

Azecine fragments are frequently presented in natural products and bioactive compounds. However, minor efforts have been devoted to these 10-membered N-heterocycles, and their synthesis is still challenging. Reported herein is the first catalytic formal [6+4] cycloaddition for the synthesis of 10-membered azecines. Under palladium catalysis, the reaction of δ-vinylvalerolactones and benzofuran-derived azadienes proceeds smoothly to afford benzofuran-fused azecines with high diastereoselectivity in moderate to good yields. A unique transannular reaction of these 10-membered azecines for the construction of polycyclic compounds is also demonstrated.

Preparation and Aromaticity of Rhenacycloprop-2-ene-containing Polycyclic Compounds

Preparation and Aromaticity of Rhenacycloprop-2-ene-containing Polycyclic Compounds