RESUMEN

This article demonstrates a late-stage modification of the cage propellanes that are transformed into intricate oxa-cycles via ring-rearrangement metathesis (RRM) and regioselective ring-closing metathesis (RCM) as crucial steps. In addition, we also report the extended pentacycloundecane (PCUD)-based oxa-cages involving the domino cycloetherification followed by olefin metathesis. These oxa-cages involve a domino sequence in which the PCUD core unit remains intact. [Ru]-based Grubbs catalysts are used to execute the metathesis step to assemble these higher-order oxa-cage systems. Spectroscopic data assigned structures of various products and were further supported by single-crystal X-ray diffraction analysis. The synthetic approach to these cage polycycles involves high complexity generating processes such as Diels-Alder reaction, [2 + 2] photocycloaddition, and RRM as well as RCM.

RESUMEN

We report late-stage ring-opening metathesis (ROM), ring-rearrangement metathesis (RRM), and ring-closing metathesis (RCM) approaches to generate expanded pentacycloundecane (PCUD) cage derivatives. These higher-order intricate polycyclic cage systems are aesthetically pleasing and structurally intriguing. Their assembly maintains molecular symmetry during the entire synthetic sequence. To this end, metathesis-based catalysts are used to execute the ROM, RRM, and RCM strategies. The synthetic approach to these cage polycycles involves the Diels-Alder reaction, [2 + 2] photocycloaddition, RRM, ROM, and RCM as key steps.

RESUMEN

Herein, we report the application of tandem ring-opening cross-metathesis (ROCM) and tandem ring-opening cross-metathesis followed by cross-metathesis (ROCM/CM) in highly strained diastereomeric heptacyclic cage diones (HCCD's) catalyzed by ruthenium catalysts. These caged diastereomeric compounds have a high degree of ring strain as well as steric congestion. Therefore, the present work related to ROCM is unique and intricate as compared to simple norbornene derivatives. It is useful to prepare new hexacyclic cage derivatives suitable for high-energy density materials. The synthetic strategy of starting cage compounds features the Diels-Alder reaction, and [2+2] photocycloaddition as key steps.

Asunto(s)

RESUMEN

Herein, we report an efficient and rapid synthetic methodology to access diversely substituted oxa-cages from unactivated olefinic substrates derived from endo-norbornenes by employing Lewis acid- (BF3 ⋅ OEt2 ) or base (NaH)-promoted intramolecular etherification. Although both BF3 ⋅ OEt2 and NaH are found to be efficient for this transformation, slightly better yields and less reaction times are achieved with NaH/DMF (0.25-1 h at 100 °C) as compared to BF3 ⋅ OEt2 /DCM (2-3 h at 0 °C to rt). The evolution of this intramolecular cyclization was studied by time-dependent NMR studies in CDCl3 solvent. Further, these observations are supported by infrared (IR) spectral data. It is worth mentioning that the present methodology enables a new route to assemble highly fused oxa-cage systems by choosing suitably substituted oxa-cage compounds for the olefin-metathesis sequence. The highly fused oxa-cage systems may have potential applications in high-energy-density materials (HEDMs) and supramolecular chemistry.

Asunto(s)

RESUMEN

A facile and efficient thiol-free one-pot method for direct synthesis of sulfides and sulfoxides under green conditions without using any metal catalyst is reported. For this purpose, we used benzyl bromides as starting materials in the presence of potassium thioacetate (PTA) and Oxone® which are low-cost, and readily accessible chemicals. This method is highly compatible with a variety of functional groups and delivered a series of sulfides, bis-sulfides, and sulfoxides in good yields. The selective formation of sulfoxides over sulfones is discussed via a mechanism.

RESUMEN

Here, we report a synthetic approach to hetero-steroids and also studied their biological activities as anticancer agents. A novel class of oxacycles containing estrone moiety were synthesized in this report. Allyl ether derived from estrone underwent Claisen rearrangement (CR) and again O-allylation and subsequent ring-closure gave A-ring-furan and oxepine fused derivatives in high yields. We used double bond isomerization and ring-closing metathesis (RCM) as key steps to assemble hetero steroids containing a mixture of regio isomers like benzofurans and benzoxepine moieties. The novel benzofuran and benzoxepine-based hybrid steroid derivatives were subjected to in vitro cytotoxicity analysis and were found to exert cancer cell-specific activity.

Asunto(s)

RESUMEN

A stereoselective [3+2] cycloaddition approach to functionalized pentaquinanes starting from cis-syn-cis triquinanes, derived from Cookson's diones, is reported. This transformation involves generation of six new stereocenters in a single step leading to cis-anti-cis-syn-cis-anti-cis polyquinane systems. Our method prevents transannular cyclizations which are prevalent in these moieties. The structure and stereochemistry of target molecules are well-characterized based on NMR data and X-ray diffraction studies.

Asunto(s)

RESUMEN

Musk analogues containing different macrocyclic ring systems as well as different annulated ring systems were synthesised by a simple and useful strategy. This strategy includes Eschenmoser-Tanabe fragmentation, enyne metathesis and Diels-Alder reaction as key steps. Starting from easily available (n) macrocyclic ketones, (n + 3) macrocyclic systems were assembled using the basic organic reactions.

RESUMEN

Benzofurans, 2H-chromenes and benzoxepines are key structural elements present in several natural products and pharmaceuticals. Here, we describe an easy-to-execute strategy for the synthesis of benzofurans, 2H-chromenes and benzoxepines, by employing Claisen rearrangement and ring-closing metathesis as key steps. A variety of phenols were converted into useful oxacycles in good to excellent yields. The ring-closing metathesis approach has been used to produce phenylpropanoid natural products. Examples described here include, the naturally occurring benzofurans such as 7-methoxywutaifuranal, 7-methoxywutaifuranol, 7-methoxywutaifuranate and the O-prenylated natural products like boropinic acid, boropinols A and C.

Asunto(s)

RESUMEN

We describe a modular approach to angularly fused polyquinanes that are core units of many natural products such as cameroonanol, subergorgic acid, and crinepellin, etc. in excellent yields by employing atom-economic ring-rearrangement metathesis as a key step. Our work highlights, the synthesis of cameroonanol analogues 1-6 and their ester derivatives by using the stereoselective reduction of the carbonyl group by using DIBAL-H- and DCC-mediated coupling as the key reactions. The subergorgic acid core 7 was produced by LDA-mediated kinetically controlled regio- and stereoselective ring-junction allylation as a critical step. Moreover, it is worth mentioning that the present strategy relies on a less explored exo-dicyclopentadiene-1-one (8) and produces highly congested polycyclic frameworks containing up to seven contiguous stereogenic centers including quaternary carbons up to two. All of the new molecules were characterized by NMR data. The structure and relative stereochemistry of some compounds were confirmed by chemical methods and further supported by single-crystal X-ray diffraction studies. The newly reported tri- and tetraquinane skeletons are present in many naturally occurring bioactive polyquinanes. Hence, this strategy is useful for designing various "druglike molecules" and expands the chemical space of cyclopentanoids that are useful in medicinal chemistry.

Asunto(s)

RESUMEN

Here, we prepared several dipeptides containing 2-aminoindane-2-carboxylic acid (Aic) and carried out further synthetic transformations. Synthesis and purification of modified peptides by using [2+2+2] cyclotrimerization is a challenging task. We are able to modify the unusual amino acids and peptide derivatives by late-stage incorporation of benzylhalo functionality. To incorporate benzylhalo moiety we used [2+2+2] cyclotrimerization in the presence of Mo(CO)6 . These halo derivatives are potential substrates for further modification by Sonogashira reaction, Suzuki-Miyaura cross-coupling, sultine formation, and the Diels-Alder reaction sequence.

RESUMEN

The title racemic triquinane, C14H14Cl2O2, is composed of four five-membered rings, one of which is a tetra-hydro-furan ring to which an allyl group on one side and a hydroxyl group on the other side are attached. The core of the triquinane unit has a cis-syn-cis configuration. In the crystal, the mol-ecules are linked by pairwise O-H⋯O hydrogen bonds, generating inversion dimers featuring R 2 2(8) loops.

RESUMEN

The title compound, C13H10O2, crystallizes with two almost planar mol-ecules in the asymmetric unit. In the crystal, slipped π-π stacking inter-actions help to establish the packing with the shortest centroid-centroid separation being 3.8195 (18) Å.

RESUMEN

The title N,N-di-methyl-thio-hydantoin containing an N-methyl-ated pthalimide group, C14H12N4O3S, arose from an unexpected reaction in a deep eutectic di-methyl-thio-urea-tartaric acid solvent system. The mean planes of the ring systems are twisted at an angle of 73.84 (17)°. In the crystal, weak C-H⋯O hydrogen bonds connect the mol-ecules.

RESUMEN

A methyl-substituted polycyclic cage dione containing the PCUD framework has undergone an unprecedented ring rearrangement approach. Here, the PCUD framework with the aid of a Lewis acid such as BF3·MeOH gave unusual fragmentation products. Two new products were isolated via the skeletal rearrangement process involving carbocation mediated intermediates. The substituents in the succinyl bond present in the strained PCUD skeleton produce a driving force for the rearrangement in an unprecedented manner. Interestingly, the cyclobutane ring was transformed to cyclopentane through the cleavage of the C1-C7 bond during the ring-expansion process of PCUD via the carbocation intermediates. Unexpectedly, solvent (benzene) was captured during the ring-homologation process due to the presence of methyl substituents placed at the cyclobutane ring of the cage framework. It appears that this is the first report where an unexpected ring-rearrangement, ring-homologation, and ring-fragmentation occur with the aid of the BF3·MeOH complex.

Asunto(s)

RESUMEN

A rapid and useful synthetic approach to various polyquinane-based natural products was accomplished efficiently by employing ring-rearrangement metathesis and ring-closing metathesis as key steps. Here, we report the synthesis of stereochemically well-defined cis-anti-cis triquinanes (1, 2), tetraquinanes (3, 4), a novel pentaquinane 5, and fused [5-5-5-6] tetracyclic systems (6, 7) that are present in crinipellin, presilphiperfolanol, cucumin, etc. Hence, the current strategy may be suitable for the synthesis of various complex natural and unnatural cyclopentanoid targets. Moreover, our approach to the newly synthesized pentaquinane 5 has paved the way for various complex polyquinanes/molecules having significant applications in theoretical and medicinal chemistry.

RESUMEN

The structure of 7-meth-oxy-penta-cyclo-[5.4.0.02,6.03,10.05,9]undecane-8,11-dione, C12H12O3, at 150 K has monoclinic (P21/c) symmetry. The penta-cyclo-undecane cage compound is composed of four five-membered rings, a planar four-membered ring and a six-membered ring in a boat conformation fused into a closed strained-cage framework. All of the five-membered rings adopt an envelope conformation.

RESUMEN

The molecular structure of the title cyclophane, C20H18O4S, has two benzyl groups, a sulfone group, and two carbonyl groups adjacent to a double bond. The phenyl rings do not show intra-molecular stacking.

RESUMEN

We report a new synthetic approach to assemble spirothiazolidinediones via a [2 + 2 + 2] cyclotrimerization reaction and the derivatives were further functionalized through DA chemistry and click reaction. Using flow cytometry, it was shown for the first time that the new benzyl alcohol derivatives of thiazolidine-2,4-dione generated here are efficient apoptosis inducers in the HeLa, Hek293, U937, Jurkat, and K562 cell lines.

RESUMEN

This account covers our work related to the development of various synthetic methodologies since 1994. We summarized our strategies and their application to design various functional molecules. In this regard, we also report the utility of our methodologies in others research work. These methods we report here are simple and efficient for the synthesis of a wide variety of intricate molecules such as heterocycles, polycycles, unusual α-amino acids, star-shaped molecules, and modified peptides. For this purpose, we used various transition metal-based reagents and catalysts. Various popular reactions such as metathesis, Suzuki coupling, [2+2+2] cyclotrimerization were used to assemble these targets. Moreover, rongalite has been used to expand the Diels-Alder chemistry.