2,222 research outputs found
Cycloaddition Chemistry for the Synthesis of Heterocyclic Compounds and Progress Towards the Total Synthesis of Grandilodine A
This thesis describes three separate research projects within the broad topic of synthetic organic chemistry. The synthesis of alkyl-substituted siloles and their reactivity in Diels-Alder chemistry is reported. Furthermore, the cleavage of the bicyclic adducts by Tamao-Fleming oxidation has been achieved which reveals a highly substituted cyclohexene-1,4-diol structure.
The second chapter describes the cycloaddition chemistry of alkoxy-activated cyclobutane dicarboxylates with aldehydes, nitrones and nitrosoarenes. The cycloaddition occurs, in the case of aldehydes, with uniformly high diastereoselectivity to afford tetrahydropyrans in good to excellent yield. When nitrones were used as the dipolarophile the cycloaddition occurs in a rather unselective manner though the formed oxazepanes undergo equilibration to yield single diastereomers in most cases. The cycloaddition with nitrosoarenes, however, proved an exception as the regioselectivity of the reaction was dependant both on the nitrosoarenes and the catalyst employed.
Lastly, progress towards the synthesis of grandilodine A is reported. Several routes were developed in attempts to form the central 8-membered ring; however successful ring closure has eluded this study
Diels-Alder chemistry of siloles and their transformation into cyclohex-2-ene-1,4-cis-diols.
The synthesis of siloles with substitution patterns that are continuative toward natural product synthesis are described. Their reactivity in Diels-Alder chemistry was explored through thermal, Lewis acid, and high-pressure reactions. Furthermore, bicyclic adducts were oxidatively cleaved to reveal a highly functionalized cyclohexene core
Are current ecological restoration practices capturing natural levels of genetic diversity? A New Zealand case study using AFLP and ISSR data from mahoe (Melicytus ramiflorus)
Sourcing plant species of local provenance (eco-sourcing) has become standard practice in plant community restoration projects. Along with established ecological restoration practices, knowledge of genetic variation in existing and restored forest fragments is important for ensuring the maintenance of natural levels of genetic variation and connectivity (gene flow) among populations. The application of restoration genetics often employs anonymous ‘fingerprinting’ markers in combination with limited sample sizes due to financial constraints. Here, we used two such marker systems, AFLPs and ISSRs, to estimate population-level genetic variation of a frequently used species in restoration projects in New Zealand, māhoe (Melicytus ramiflorus, Violaceae). We examined two rural and two urban forest fragments, as potential local source populations, to determine whether the māhoe population at the recently (re)constructed ecosystem at Waiwhakareke Natural Heritage Park (WNHP), Hamilton, New Zealand reflects the genetic variation observed in these four potential source populations. Both marker systems produced similar results and indicated, even with small population sizes, that levels of genetic variation at WNHP were comparable to in situ populations. However, the AFLPs did provide finer resolution of the population genetic structure than ISSRs. ISSRs, which are less expensive and technically less demanding to generate than AFLPs, may be sufficient for restoration projects where only a broad level of genotypic resolution is required. We recommend the use of AFLPs when species with a high conservation status are being used due to the greater resolution of this technique
The formal [4+3] cycloaddition between donor-acceptor cyclobutanes and nitrones.
The formal [4+3] cycloaddition of 2-alkoxy-1,1-dicarboxylate activated donor-acceptor cyclobutanes with nitrones is disclosed. The reaction forms structurally unique oxazepines in moderate to high yield with a wide scope of nitrones. In most cases either a diastereomeric mixture or a single diastereomer may be formed, depending on the reaction conditions
The [4+2] cycloaddition of donor-acceptor cyclobutanes and nitrosoarenes.
The Yb(OTf)3 catalyzed [4+2] cycloaddition between donor-acceptor cyclobutanes and nitrosoarenes is disclosed. This method facilitates the synthesis of tetrahydro-1,2-oxazines in good to excellent yields as single diastereomers. Except for a few electron-deficient nitrosoarenes, excellent regioselectivity was observed throughout these studies
Synthesis of (+)-Bovidic Acid
(+)-Bovidic acid is an 18-carbon hydroxyfuranoid acid isolated from the pelage of the gaur (Bosfrontalis) and displays potential as an insect repellant. Both a formal and total synthesis of (+)-bovidic acid was carried out with the core of the natural product being synthesized through Mukaiyama aerobic oxidative cyclization employing the second-generation Co(nmp)2 catalyst
An electrostatic mechanism for Ca(2+)-mediated regulation of gap junction channels.
Gap junction channels mediate intercellular signalling that is crucial in tissue development, homeostasis and pathologic states such as cardiac arrhythmias, cancer and trauma. To explore the mechanism by which Ca(2+) blocks intercellular communication during tissue injury, we determined the X-ray crystal structures of the human Cx26 gap junction channel with and without bound Ca(2+). The two structures were nearly identical, ruling out both a large-scale structural change and a local steric constriction of the pore. Ca(2+) coordination sites reside at the interfaces between adjacent subunits, near the entrance to the extracellular gap, where local, side chain conformational rearrangements enable Ca(2+)chelation. Computational analysis revealed that Ca(2+)-binding generates a positive electrostatic barrier that substantially inhibits permeation of cations such as K(+) into the pore. Our results provide structural evidence for a unique mechanism of channel regulation: ionic conduction block via an electrostatic barrier rather than steric occlusion of the channel pore
Formal [4 + 2] cycloaddition of alkoxy-substituted donor-acceptor cyclobutanes and aldehydes catalyzed by Yb(OTf)3.
The cycloaddition between 2-alkoxy-1,1-cyclobutane diesters and aromatic, heteroaromatic, or aliphatic aldehydes under Yb(OTf)(3) catalysis generates tetrahydropyrans in high yields with exclusive cis-stereochemistry
Zoochorous dispersal of freshwater bivalves: an overlooked vector in biological invasions?
Vectors that underpin the natural dispersal of invasive alien species are frequently unknown. In particular, the passive dispersal (zoochory) of one organism (or propagule) by another, usually more mobile animal, remains poorly understood. Field observations of the adherence of invasive freshwater bivalves to other organisms have prompted us to assess the importance of zoochory in the spread of three prolific invaders: zebra mussel Dreissena polymorpha; quagga mussel Dreissena bugensis; and Asian clam Corbicula fluminea. An extensive, systematic search of the literature was conducted across multiple on-line scientific databases using various search terms and associated synonyms. In total, only five publications fully satisfied the search criteria. It appears that some fish species can internally transport viable adult D. polymorpha and C. fluminea specimens. Additionally, literature indicates that veligers and juvenile D. polymorpha can adhere to the external surfaces of waterbirds. Overall, literature suggests that zoochorous dispersal of invasive bivalves is possible, but likely a rare occurrence. However, even the establishment of a few individuals (or a single self-fertilising C. fluminea specimen) can, over-time, result in a substantial population. Here, we highlight knowledge gaps, identify realistic opportunities for data collection, and suggest management protocols to mitigate the spread of invasive alien species
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