Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Access to Highly Strained Tricyclic Ketals Derived from Coumarins.

ABSTRACT: Synthesis of highly strained fused substituted dihydrobenzopyran cyclopropyl lactones derived from coumarin carboxylates are reported. The substrate scope tolerates a variety of 6- and 8-substituents on the coumarin ring. Substitution at the 5- or 7-position is resistant to tricyclic lactone formation except with 7-methyl substitution. Benzamide-containing coumarins afford the tricyclic ketal. A plausible mechanism is proposed for the formation of the fused lactone: intramolecular rearrangement of trans cyclopropyl methyl ketones with phenolic acetate via the formation of a hemiacetal.

SUBMITTER: Jonnalagadda SK

PROVIDER: S-EPMC8996706 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Access to Highly Strained Tricyclic Ketals Derived from Coumarins.

Jonnalagadda Sravan K SK Huwaimel Bader I BI Jonnalagadda Shirisha S Garrison Jered C JC Trippier Paul C PC

The Journal of organic chemistry 20220308 6

Synthesis of highly strained fused substituted dihydrobenzopyran cyclopropyl lactones derived from coumarin carboxylates are reported. The substrate scope tolerates a variety of 6- and 8-substituents on the coumarin ring. Substitution at the 5- or 7-position is resistant to tricyclic lactone formation except with 7-methyl substitution. Benzamide-containing coumarins afford the tricyclic ketal. A plausible mechanism is proposed for the formation of the fused lactone: intramolecular rearrangement ...[more]

PMID: 35258961

Similar Datasets

An Enantiospecific Synthesis of Isoneoamphilectane Confirms Its Strained Tricyclic Structure.

Project description:We describe a total synthesis of the rare isocyanoterpene natural product isoneoamphilectane and two of its unnatural diastereomers. The significantly strained ring system of the reported natural product─along with a hypothesis about a biosynthetic relationship to related family members─inspired us to consider a potential misassignment in the structure's relative configuration. As a result, we initially targeted two less strained, more accessible, stereoisomers of the reported natural product. When these compounds failed to exhibit spectroscopic data that matched those of isoneoamphilectane, we embarked on a synthesis of the originally proposed strained structure via an approach that hinged on a challenging cis-to-trans decalone epimerization. Ultimately, we implemented a novel cyclic sulfite pinacol-type rearrangement to generate the strained ring system. Additional features of this work include the application of a stereocontrolled Mukaiyama-Michael addition of an acyclic silylketene acetal, an unusual intramolecular alkoxide-mediated regioselective elimination, and an HAT-mediated alkene hydroazidation to forge the C-N bond of the tertiary isonitrile. Throughout this work, our synthetic planning was heavily guided by computational analyses to inform on key issues of stereochemical control.

| S-EPMC9936588 | biostudies-literature

Enzymatic construction of highly strained carbocycles.

Project description:Small carbocycles are structurally rigid and possess high intrinsic energy due to their ring strain. These features lead to broad applications but also create challenges for their construction. We report the engineering of hemeproteins that catalyze the formation of chiral bicyclobutanes, one of the most strained four-membered systems, via successive carbene addition to unsaturated carbon-carbon bonds. Enzymes that produce cyclopropenes, putative intermediates to the bicyclobutanes, were also identified. These genetically encoded proteins are readily optimized by directed evolution, function in Escherichia coli, and act on structurally diverse substrates with high efficiency and selectivity, providing an effective route to many chiral strained structures. This biotransformation is easily performed at preparative scale, and the resulting strained carbocycles can be derivatized, opening myriad potential applications.

| S-EPMC6104391 | biostudies-literature

Highly tensile-strained Ge/InAlAs nanocomposites.

Project description:Self-assembled nanocomposites have been extensively investigated due to the novel properties that can emerge when multiple material phases are combined. Growth of epitaxial nanocomposites using lattice-mismatched constituents also enables strain-engineering, which can be used to further enhance material properties. Here, we report self-assembled growth of highly tensile-strained Ge/In0.52Al0.48As (InAlAs) nanocomposites by using spontaneous phase separation. Transmission electron microscopy shows a high density of single-crystalline germanium nanostructures coherently embedded in InAlAs without extended defects, and Raman spectroscopy reveals a 3.8% biaxial tensile strain in the germanium nanostructures. We also show that the strain in the germanium nanostructures can be tuned to 5.3% by altering the lattice constant of the matrix material, illustrating the versatility of epitaxial nanocomposites for strain engineering. Photoluminescence and electroluminescence results are then discussed to illustrate the potential for realizing devices based on this nanocomposite material.

| S-EPMC5290139 | biostudies-literature

Convenient access to bicyclic and tricyclic diazenes.

Project description:Heating the tosylhydrazone of an omega-alkenyl ketone or aldehyde to reflux in toluene in the presence of K(2)CO(3) delivered the bicyclic diazene. Irradiation of the diazene converted it to the cyclopropane. This appears to be a generally useful method for the construction of substituted cyclopentanes and cyclohexanes.

| S-EPMC2765546 | biostudies-literature

Quadrupolar Dyes Based on Highly Polarized Coumarins.

Project description:The fluorescence and other photophysical parameters of highly polarized, quadrupolar bis-coumarins possessing an electron-rich pyrrolo[3,2-b]pyrrole bridging unit are highly dependent on the linking position between both chromophores. Delocalization of the LUMO on the entire π-system results in intense emission and strong two-photon absorption.

| S-EPMC8419859 | biostudies-literature

Highly Biaxially Strained Silicene on Au(111).

Project description:Many of graphene's remarkable properties arise from its linear dispersion of the electronic states, forming a Dirac cone at the K points of the Brillouin zone. Silicene, the 2D allotrope of silicon, is also predicted to show a similar electronic band structure, with the addition of a tunable bandgap, induced by spin-orbit coupling. Because of these outstanding electronic properties, silicene is considered as a promising building block for next-generation electronic devices. Recently, it has been shown that silicene grown on Au(111) still possesses a Dirac cone, despite the interaction with the substrate. Here, to fully characterize the structure of this 2D material, we investigate the vibrational spectrum of a monolayer silicene grown on Au(111) by polarized Raman spectroscopy. To enable a detailed ex situ investigation, we passivated the silicene on Au(111) by encapsulating it under few layers hBN or graphene flakes. The observed spectrum is characterized by vibrational modes that are strongly red-shifted with respect to the ones expected for freestanding silicene. By comparing low-energy electron diffraction (LEED) patterns and Raman results with first-principles calculations, we show that the vibrational modes indicate a highly (>7%) biaxially strained silicene phase.

| S-EPMC8154839 | biostudies-literature

Entropy-driven crystal formation on highly strained substrates.

Project description:In heteroepitaxy, lattice mismatch between the deposited material and the underlying surface strongly affects nucleation and growth processes. The effect of mismatch is well studied in atoms with growth kinetics typically dominated by bond formation with interaction lengths on the order of one lattice spacing. In contrast, less is understood about how mismatch affects crystallization of larger particles, such as globular proteins and nanoparticles, where interparticle interaction energies are often comparable to thermal fluctuations and are short ranged, extending only a fraction of the particle size. Here, using colloidal experiments and simulations, we find particles with short-range attractive interactions form crystals on isotropically strained lattices with spacings significantly larger than the interaction length scale. By measuring the free-energy cost of dimer formation on monolayers of increasing uniaxial strain, we show the underlying mismatched substrate mediates an entropy-driven attractive interaction extending well beyond the interaction length scale. Remarkably, because this interaction arises from thermal fluctuations, lowering temperature causes such substrate-mediated attractive crystals to dissolve. Such counterintuitive results underscore the crucial role of entropy in heteroepitaxy in this technologically important regime. Ultimately, this entropic component of lattice mismatched crystal growth could be used to develop unique methods for heterogeneous nucleation and growth of single crystals for applications ranging from protein crystallization to controlling the assembly of nanoparticles into ordered, functional superstructures. In particular, the construction of substrates with spatially modulated strain profiles would exploit this effect to direct self-assembly, whereby nucleation sites and resulting crystal morphology can be controlled directly through modifications of the substrate.

| S-EPMC3677474 | biostudies-literature

Vibrational Properties in Highly Strained Hexagonal Boron Nitride Bubbles.

Project description:Hexagonal boron nitride (hBN) is widely used as a protective layer for few-atom-thick crystals and heterostructures (HSs), and it hosts quantum emitters working up to room temperature. In both instances, strain is expected to play an important role, either as an unavoidable presence in the HS fabrication or as a tool to tune the quantum emitter electronic properties. Addressing the role of strain and exploiting its tuning potentiality require the development of efficient methods to control it and of reliable tools to quantify it. Here we present a technique based on hydrogen irradiation to induce the formation of wrinkles and bubbles in hBN, resulting in remarkably high strains of ∼2%. By combining infrared (IR) near-field scanning optical microscopy and micro-Raman measurements with numerical calculations, we characterize the response to strain for both IR-active and Raman-active modes, revealing the potential of the vibrational properties of hBN as highly sensitive strain probes.

| S-EPMC8880391 | biostudies-literature

Primitive Path Analysis and Stress Distribution in Highly Strained Macromolecules.

Project description:Polymer material properties are strongly affected by entanglement effects. For long polymer chains and composite materials, they are expected to be at the origin of many technically important phenomena, such as shear thinning or the Mullins effect, which microscopically can be related to topological constraints between chains. Starting from fully equilibrated highly entangled polymer melts, we investigate the effect of isochoric elongation on the entanglement structure and force distribution of such systems. Theoretically, the related viscoelastic response usually is discussed in terms of the tube model. We relate stress relaxation in the linear and nonlinear viscoelastic regimes to a primitive path analysis (PPA) and show that tension forces both along the original paths and along primitive paths, that is, the backbone of the tube, in the stretching direction correspond to each other. Unlike homogeneous relaxation along the chain contour, the PPA reveals a so far not observed long-lived clustering of topological constraints along the chains in the deformed state.

| S-EPMC5828704 | biostudies-literature

Low-threshold optically pumped lasing in highly strained germanium nanowires.

Project description:The integration of efficient, miniaturized group IV lasers into CMOS architecture holds the key to the realization of fully functional photonic-integrated circuits. Despite several years of progress, however, all group IV lasers reported to date exhibit impractically high thresholds owing to their unfavourable bandstructures. Highly strained germanium with its fundamentally altered bandstructure has emerged as a potential low-threshold gain medium, but there has yet to be a successful demonstration of lasing from this seemingly promising material system. Here we demonstrate a low-threshold, compact group IV laser that employs a germanium nanowire under a 1.6% uniaxial tensile strain as the gain medium. The amplified material gain in strained germanium can sufficiently overcome optical losses at 83 K, thus allowing the observation of multimode lasing with an optical pumping threshold density of ~3.0 kW cm-2. Our demonstration opens new possibilities for group IV lasers for photonic-integrated circuits.

| S-EPMC5705600 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data