scholarly journals Identification, synthesis and mass spectrometry of a macrolide from the African reed frog Hyperolius cinnamomeoventris

2016 ◽  
Vol 12 ◽  
pp. 2731-2738 ◽  
Author(s):  
Markus Menke ◽  
Pardha Saradhi Peram ◽  
Iris Starnberger ◽  
Walter Hödl ◽  
Gregory FM Jongsma ◽  
...  
Keyword(s):  
Mass Spectrum ◽  
Double Bond ◽  
Fragmentation Pathway ◽  
Ring Closing Metathesis ◽  
Grubbs Catalyst ◽  
Open Chain ◽  
Naturally Occurring ◽  
Products Analysis ◽  
First Time ◽  
Gular Glands

The contents of the gular glands of the male African reed frog Hyperolius cinnamomeoventris consist of a mixture of aliphatic macrolides and sesquiterpenes. While the known macrolide gephyromantolide A was readily identified, the structure of another major component was suggested to be a tetradecen-13-olide. The synthesis of the two candidate compounds (Z)-5- and (Z)-9-tetradecen-13-olide revealed the former to be the naturally occurring compound. The synthesis used ring-closing metathesis as key step. While the Hoveyda–Grubbs catalyst furnished a broad range of isomeric products, the (Z)-selective Grubbs catalyst lead to pure (Z)-products. Analysis by chiral GC revealed the natural frog compound to be (5Z,13S)-5-tetradecen-13-olide (1). This compound is also present in the secretion of other hyperoliid frogs as well as in femoral glands of male mantellid frogs such as Spinomantis aglavei. The mass spectra of the synthesized macrolides as well as their rearranged isomers obtained during ring-closing metathesis showed that it is possible to assign the location of the double bond in an unsaturated macrolide on the basis of its EI mass spectrum. The occurrence of characteristic ions can be explained by the fragmentation pathway proposed in the article. In contrast, the localization of a double bond in many aliphatic open-chain compounds like alkenes, alcohols or acetates, important structural classes of pheromones, is usually not possible from an EI mass spectrum. In the article, we present the synthesis and for the first time elucidate the structure of macrolides from the frog family Hyperoliidae.

scholarly journals ATOMIC STRUCTURES OF GLUCOSE, FRUCTOSE AND SUCROSE AND EXPLANATION OF ANOMERIC CARBON

2014 ◽  
Author(s):  
Raji Heyrovska
Keyword(s):  
Double Bond ◽  
Single Bond ◽  
Open Chain ◽  
Bond Lengths ◽  
Atomic Structures ◽  
Anomeric Carbon ◽  
First Time ◽  
Atomic Radii

Presented here are the structures of three biologically important sweet sugars, based on the additivity of covalent atomic radii in bond lengths. The observed smaller carbon-oxygen distances involving the 'anomeric' carbons of the open chain hexoses are explained here, for the first time, as due to the smaller covalent double bond radii of carbon and oxygen than their single bond radii in the cyclic forms and in sucrose. The atomic structures of all the three carbohydrates, drawn to scale in colour, have been presented here also for the first time.

A Novel Scheme for the Synthesis of 21-Acetoxypregna-1,4,9(11)-triene- 17α,21-diol-3,20-dione from 9α-Hydroxyandrostenedione

2020 ◽  
Vol 16 (5) ◽  
pp. 606-610
Author(s):  
Nguyen T. Diep ◽  
Luu D. Huy
Keyword(s):  
Double Bond ◽  
Chemical Synthesis ◽  
Economic Efficiency ◽  
Final Stage ◽  
Side Chain ◽  
Entire Process ◽  
Drug Synthesis ◽  
First Time

Background: Vietnam currently imports up to 90% of the pharmaceuticals it consumes and 100% of the steroid-based pharmaceuticals. The ability for efficient chemical synthesis of the steroids could create commercial opportunities to address this issue. Synthesis of 21-acetoxypregna-1,4,9(11)- triene-17α,21-diol-3,20-dione is considered a key intermediate in the scheme of steroidal drug synthesis. Previous synthesis attempts of such steroids (corticoids) introduce a double bond at C-1(2) in the final stage of synthesis, which delivers a poor yield and reduces the economic efficiency of the process. Objective: To study and develop a novel and effective method for the synthesis of 21-acetoxypregna- 1,4,9(11)-triene-17α,21-diol-3,20-dione. Methods: Using 9α-hydroxyandrostenedione as a substrate chemical synthesis was performed as follows: pregnane side chain construction at C-17 (acetylene method), introduction of C-1(2) double bond (using SeO2), epimerization of C-17 (via 17-ONO2 ester) and Stork’s iodination. Results: 21-acetoxypregna-1,4,9(11)-triene-17α,21-diol-3,20-dione was prepared from 9α- hydroxyandrostenedione with an improved yield compared to previous attempts. Conclusion: Here, 21-acetoxypregna-1,4,9(11)-triene-17α,21-diol-3,20-dione has been synthesized from 9α-hydroxyandrostenedione based on a novel, effective and commercially feasible scheme. The introduction of the C-1(2) double bond at an earlier stage of the synthesis has increased the economic efficiency of the entire process. For the first time, the indirect epimerization mechanism has been clarified along with the configuration of the C-17 stereo-center which has been confirmed using NOESY data.

scholarly journals An event excess observed in the deeply bound region of the 12C (K−, p) missing-mass spectrum

2020 ◽  
Vol 2020 (12) ◽  
Author(s):  
Yudai Ichikawa ◽  
Junko Yamagata-Sekihara ◽  
Jung Keun Ahn ◽  
Yuya Akazawa ◽  
Kanae Aoki ◽  
...  
Keyword(s):  
Mass Spectrum ◽  
Binding Energy ◽  
Decay Channel ◽  
Peak Shift ◽  
Bound State ◽  
Elastic Peak ◽  
Missing Mass ◽  
Decay Modes ◽  
Kaon Momentum ◽  
First Time

Abstract We have measured, for the first time, the inclusive missing-mass spectrum of the $^{12}$C$(K^-, p)$ reaction at an incident kaon momentum of 1.8 GeV/$c$ at the J-PARC K1.8 beamline. We observed a prominent quasi-elastic peak ($K^-p \rightarrow K^-p$) in this spectrum. In the quasi-elastic peak region, the effect of secondary interaction is apparently observed as a peak shift, and the peak exhibits a tail in the bound region. We compared the spectrum with a theoretical calculation based on the Green’s function method by assuming different values of the parameters for the $\bar{K}$–nucleus optical potential. We found that the spectrum shape in the binding-energy region $-300 \, \text{MeV} < B_{K} < 40$ MeV is best reproduced with the potential depths $V_0 = -80$ MeV (real part) and $W_0 = -40$ MeV (imaginary part). On the other hand, we observed a significant event excess in the deeply bound region around $B_{K} \sim 100$ MeV, where the major decay channel of $K^- NN \to \pi\Sigma N$ is energetically closed, and the non-mesonic decay modes ($K^- NN \to \Lambda N$ and $\Sigma N$) should mainly contribute. The enhancement is fitted well by a Breit–Wigner function with a kaon-binding energy of 90 MeV and width 100 MeV. A possible interpretation is a deeply bound state of a $Y^{*}$-nucleus system.

Synthesis of coumarins by ring-closing metathesis using Grubbs’ catalyst

2003 ◽  
Vol 44 (22) ◽  
pp. 4199-4201 ◽  
Author(s):  
Tuyen Nguyen Van ◽  
Silvia Debenedetti ◽  
Norbert De Kimpe
Keyword(s):  
Ring Closing Metathesis ◽  
Grubbs Catalyst

New pseudohalide ligands in Ru-catalyzed olefin metathesis — A robust, air-activated iminopyrrolato catalyst

2005 ◽  
Vol 83 (6-7) ◽  
pp. 748-754 ◽  
Author(s):  
Samantha D Drouin ◽  
Heather M Foucault ◽  
Glenn PA Yap ◽  
Deryn E Fogg
Keyword(s):  
Key Words ◽  
Olefin Metathesis ◽  
High Reactivity ◽  
Ring Closing Metathesis ◽  
Grubbs Catalyst ◽  
X Ray ◽  
X Ray Crystallography

Reaction of the Grubbs catalyst RuCl2(PCy3)2(CHPh) (1) with lithium 2-[(2,6-diisopropylphenyl)imino]pyrrolide·Et2O (LiNN′·Et2O) gives alkylidene complex 5, containing a chelating, σ-bound iminopyrrolato unit. The structure of 5 is confirmed by X-ray crystallography. Treatment of 5 with pyridine generates RuCl(NN′)(py)2(CHPh) (6) via displacement of PCy3. Complex 5 effects ring-closing metathesis in air, displaying high reactivity relative to 6.Key words: ruthenium, alkylidene, metathesis, pyrrolimine, iminopyrrolato.

scholarly journals Microbialite-like structures in Cladophora sp. (Ulvophyceae) mats from a subtropical Andean basin: ecological implications

2019 ◽  
Vol 67 (1) ◽  
Author(s):  
Hugo R. Fernández ◽  
Ana Lucia Gonzalez Achem ◽  
Marcela Correa ◽  
Virginia H. Albarracín
Keyword(s):  
Organic Pollution ◽  
Biological Factors ◽  
X Ray Diffraction ◽  
Calcite Precipitation ◽  
Annual Cycles ◽  
X Ray ◽  
Naturally Occurring ◽  
Ecological Implications ◽  
First Time ◽  
Solubility Equilibrium

The solubility equilibrium of calcite is influenced by physicochemical, climatic and biological factors. Annual cycles of exceptionally prolonged drought, in conjunction with naturally occurring diffuse organic pollution, generate the unique conditions for the precipitation of lithified carbonate structures (microbialites). The aim of this article is to analyze the possible implications of calcite precipitation produced in mats of Cladophora sp. in an Andean subtropical basin, considering it is the first time this phenomenon is described for the region. We collected samples from selected sites at the Lules River Basin, in four sampling dates between the years 2003 and 2004, within a monitoring work of 15 years. Samples were analyzed using an electron microscope and X-ray diffraction analysis. We found that Gomphonema sp. attached to Cladophora sp. contributes to precipitation of calcite and formation of microbialite like structures, in the studied area. This work presents an initial discussion of the discovery of microbialites-like structures attached to Cladophora sp. mats in a subtropical Andean stream and the environmental conditions that lead to their production, as well as the possible ecological implications of these microbialites.

scholarly journals Ring-closing-metathesis-based synthesis of annellated coumarins from 8-allylcoumarins

2018 ◽  
Vol 14 ◽  
pp. 2991-2998 ◽  
Author(s):  
Christiane Schultze ◽  
Bernd Schmidt
Keyword(s):  
Double Bond ◽  
Olefin Metathesis ◽  
Claisen Rearrangement ◽  
Allylic Oxidation ◽  
Allyl Ether ◽  
Ring Closing Metathesis ◽  
Wittig Olefination

8-Allylcoumarins are conveniently accessible through a microwave-promoted tandem Claisen rearrangement/Wittig olefination/cyclization sequence. They serve as a versatile platform for the annellation of five- to seven-membered rings using ring-closing olefin metathesis (RCM). Furano-, pyrano-, oxepino- and azepinocoumarins were synthesized from the same set of precursors using Ru-catalyzed double bond isomerizations and RCM in a defined order. One class of products, pyrano[2,3-f]chromene-2,8-diones, were inaccessible through direct RCM of an acrylate, but became available from the analogous allyl ether via an assisted tandem catalytic RCM/allylic oxidation sequence.

scholarly journals Pharmacologic Activities¬ of 3’-Hydroxypterostilbene: Cytotoxic, Anti-Oxidant, Anti-Adipogenic, Anti-Inflammatory, Histone Deacetylase and Sirtuin 1 Inhibitory Activity

2015 ◽  
Vol 18 (4) ◽  
pp. 713 ◽  
Author(s):  
Jody K Takemoto ◽  
Connie M. Remsberg ◽  
Neal M. Davies
Keyword(s):  
Histone Deacetylase ◽  
Inhibitory Activity ◽  
Sirtuin 1 ◽  
In Vitro Assays ◽  
Naturally Occurring ◽  
Anti Oxidant ◽  
Anti Inflammatory ◽  
First Time ◽  
Stilbene Compounds

Purpose: Delineate the selected pharmacodynamics of a naturally occurring stilbene 3’-Hydroxypterostilbene. Objective: Characterize for the first time the pharmacodynamics bioactivity in several in-vitro assays with relevant roles in heart disease, inflammation, cancer, and diabetes etiology and pathophysiology. Methods: 3’-Hydroxypterostilbene was studied in in-vitro assays to identify possible bioactivity. Results: 3’-Hydroxypterostilbene demonstrated anti-oxidant, anti-inflammatory, cytotoxic, anti-adipogenic, histone deacetylase, and sirtuin-1 inhibitory activity. Conclusions: The importance of understanding individual stilbene pharmacologic activities were delineated.  Small changes in chemical structure of stilbene compounds result in significant pharmacodynamic differences. This article is open to POST-PUBLICATION REVIEW. Registered readers (see “For Readers”) may comment by clicking on ABSTRACT on the issue’s contents page.

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