| fullrecord |
[{"key": "dc.contributor.advisor", "value": "Pihko, Petri", "language": "", "element": "contributor", "qualifier": "advisor", "schema": "dc"}, {"key": "dc.contributor.advisor", "value": "Rolig, Aino", "language": "", "element": "contributor", "qualifier": "advisor", "schema": "dc"}, {"key": "dc.contributor.advisor", "value": "Mondal, Pradip", "language": "", "element": "contributor", "qualifier": "advisor", "schema": "dc"}, {"key": "dc.contributor.author", "value": "Stenfors, Sanna", "language": "", "element": "contributor", "qualifier": "author", "schema": "dc"}, {"key": "dc.date.accessioned", "value": "2024-12-11T06:40:30Z", "language": null, "element": "date", "qualifier": "accessioned", "schema": "dc"}, {"key": "dc.date.available", "value": "2024-12-11T06:40:30Z", "language": null, "element": "date", "qualifier": "available", "schema": "dc"}, {"key": "dc.date.issued", "value": "2024", "language": "", "element": "date", "qualifier": "issued", "schema": "dc"}, {"key": "dc.identifier.uri", "value": "https://jyx.jyu.fi/handle/123456789/98921", "language": null, "element": "identifier", "qualifier": "uri", "schema": "dc"}, {"key": "dc.description.abstract", "value": "T\u00e4m\u00e4n pro gradu- tutkielman kirjallinen osa keskittyy keskikokoisten rengasrakenteisten yhdisteiden ominaisuuksiin, stereoselektiivisiin synteesistrategioihin, \nesiintyvyyteen luonnonaineissa, sek\u00e4 hy\u00f6dynt\u00e4miseen l\u00e4\u00e4keainekemiassa. Kokeellisessa osassa tutkittiin \nfotokemiallista Cope toisiintumista mahdollisena uutena menetelm\u00e4n\u00e4 trisubstituoitujen alkeenien stereoselektiiviseen synteesiin. \n\nKirjallisen osan alkup\u00e4\u00e4ss\u00e4 k\u00e4sitell\u00e4\u00e4n esim. keskikokoisten renkaiden j\u00e4ykist\u00e4vi\u00e4 elementtej\u00e4, \nstereokemiaa sek\u00e4 konformaatioanalyysi\u00e4. Keskikokoisten renkaiden synteesi orgaanisessa kemiassa on hyvin vaikeaa mm. j\u00e4nnittyneen rakenteen, destabiloivien transannulaaristen vuorovaikutusten sek\u00e4 syklisaatioreaktioissa tapahtuvan entropian pieneneminen vuoksi. Kolmannessa luvussa k\u00e4sitell\u00e4\u00e4n esimerkkej\u00e4 renkaanlaajennus- ja syklisaatioreaktioista, joiden avulla on syntetisoitu keskikokoisia renkaita stereoselektiivisesti. Luvussa 4 esitell\u00e4\u00e4n keskikokoisen renkaan sis\u00e4lt\u00e4vi\u00e4 \nkarbo- ja heterosyklisi\u00e4 yhdisteit\u00e4 l\u00e4\u00e4keainesuunnittelussa/l\u00e4\u00e4keainekemian n\u00e4k\u00f6kulmasta. \n\nSynteesiin liittyvist\u00e4 vaikeuksista huolimatta keskikokoiset renkaat ovat hyvin mielenkiintoisia rakenneyksik\u00f6it\u00e4 l\u00e4\u00e4keaineissa, mik\u00e4 on lis\u00e4nnyt kiinnostusta synteesimenetelmien kehitt\u00e4miseen. Lis\u00e4ksi esim. 8- ja 9-j\u00e4senisi\u00e4 renkaita esiintyy useissa luonnonaineissa kuten \nseskviterpeeneihin kuuluvassa karyofylleenissa, joka syntetisoitiin ensimm\u00e4isen kerran vuonna 1963. Keskikokoisten renkaiden synteesimenetelmien kehitys jatkuu edelleen, esimerkiksi Petri Pihkon tutkimusryhm\u00e4n synteesikohteena oleva humiliisini E on 9-renkaan sis\u00e4lt\u00e4v\u00e4 \nmakrosykli. \n\nT\u00e4m\u00e4n tutkielman kokeellisessa osassa toteutettiin funktionalisoidun keskikokoisen renkaan l\u00e4ht\u00f6aineen synteesi k\u00e4ytt\u00e4m\u00e4ll\u00e4 fotokemiallista isomerisaatiota avainvaiheena. L\u00e4ht\u00f6aineen hiilirunko syntetisoitiin alkylaation ja Weinreb-ketoni-synteesin avulla. Fotokemiallinen isomerisaatio onnistui, mutta reaktio ei ollut t\u00e4ysin stereoselektiivinen. Isomerisaatioreaktion p\u00e4\u00e4tuotteena saatiin funktionalisoitua trisubstituoitua Z-alkeenia, jota voitaisi edelleen hy\u00f6dynt\u00e4\u00e4 10-renkaisen laktonin synteesiin.", "language": "fi", "element": "description", "qualifier": "abstract", "schema": "dc"}, {"key": "dc.description.abstract", "value": "The literature review section of this master's thesis focuses on the properties of compounds with medium-sized rings, stereoselective synthesis strategies, occurrence in natural products, and utilization in medicinal chemistry. In the experimental part, the photochemical Cope rearrangement was explored as a potential new method for the stereoselective synthesis of \ntrisubstituted alkenes. \n\nThe beginning of the literature review discusses, for example, the rigidifying elements of medium-sized rings, stereochemistry, and conformational analysis. The synthesis of medium-sized rings in organic chemistry is very difficult, for example, due to the strained structure, \ndestabilizing transannular interactions, and lowering of entropy in the cyclization reaction. The third chapter discusses examples of ring expansion and cyclization strategies that have been used to synthesize medium-sized rings stereoselectively. Lastly, carbo- and heterocyclic compounds containing medium-sized rings are presented from the perspective of medicinal chemistry and their applications. \n\nDespite the difficulties associated with synthesis, medium-sized rings are very interesting structural units in the design of pharmaceuticals. This feature has increased interest in the development of synthesis methods. In addition, medium-sized rings, such as 8- and 9-membered rings are found in several natural products. An example is the sesquiterpene caryophyllene, which was synthesized for the first time in 1963. The development of synthetic \nmethods for medium-sized rings continues today. In current research, humilisin E, a macrocycle containing a 9-membered ring is a target of total synthesis in the research group of Petri Pihko. \n\nIn the experimental part of this thesis, a functionalized starting material for medium-sized ring synthesis was prepared using a photochemical isomerization reaction as the key step. The carbon backbone of the starting material was synthesized by alkylation and Weinreb ketone synthesis. The photochemical isomerization was successful, but the reaction was not completely stereoselective, and a functionalized trisubstituted Z-alkene was obtained as the major product.", "language": "en", "element": "description", "qualifier": "abstract", "schema": "dc"}, {"key": "dc.description.provenance", "value": "Submitted by Paivi Vuorio (paelvuor@jyu.fi) on 2024-12-11T06:40:30Z\nNo. of bitstreams: 0", "language": "en", "element": "description", "qualifier": "provenance", "schema": "dc"}, {"key": "dc.description.provenance", "value": "Made available in DSpace on 2024-12-11T06:40:30Z (GMT). No. of bitstreams: 0\n Previous issue date: 2024", "language": "en", "element": "description", "qualifier": "provenance", "schema": "dc"}, {"key": "dc.format.extent", "value": "186", "language": "", "element": "format", "qualifier": "extent", "schema": "dc"}, {"key": "dc.language.iso", "value": "eng", "language": null, "element": "language", "qualifier": "iso", "schema": "dc"}, {"key": "dc.rights", "value": "In Copyright", "language": "en", "element": "rights", "qualifier": null, "schema": "dc"}, {"key": "dc.subject.other", "value": "medium-sized rings", "language": "", "element": "subject", "qualifier": "other", "schema": "dc"}, {"key": "dc.subject.other", "value": "pharmaceuticals", "language": "", "element": "subject", "qualifier": "other", "schema": "dc"}, {"key": "dc.subject.other", "value": "macrocycles", "language": "", "element": "subject", "qualifier": "other", "schema": "dc"}, {"key": "dc.subject.other", "value": "photo-Cope rearrangement", "language": "", "element": "subject", "qualifier": "other", "schema": "dc"}, {"key": "dc.title", "value": "Rigid medium-sized rings : applications and synthesis", "language": "", "element": "title", "qualifier": null, "schema": "dc"}, {"key": "dc.type", "value": "master thesis", "language": null, "element": "type", "qualifier": null, "schema": "dc"}, {"key": "dc.identifier.urn", "value": "URN:NBN:fi:jyu-202412117734", "language": null, "element": "identifier", "qualifier": "urn", "schema": "dc"}, {"key": "dc.type.ontasot", "value": "Master\u2019s thesis", "language": "en", "element": "type", "qualifier": "ontasot", "schema": "dc"}, {"key": "dc.type.ontasot", "value": "Pro gradu -tutkielma", "language": "fi", "element": "type", "qualifier": "ontasot", "schema": "dc"}, {"key": "dc.contributor.faculty", "value": "Matemaattis-luonnontieteellinen tiedekunta", "language": "fi", "element": "contributor", "qualifier": "faculty", "schema": "dc"}, {"key": "dc.contributor.faculty", "value": "Faculty of Sciences", "language": "en", "element": "contributor", "qualifier": "faculty", "schema": "dc"}, {"key": "dc.contributor.department", "value": "Kemian laitos", "language": "fi", "element": "contributor", "qualifier": "department", "schema": "dc"}, {"key": "dc.contributor.department", "value": "Department of Chemistry", "language": "en", "element": "contributor", "qualifier": "department", "schema": "dc"}, {"key": "dc.contributor.organization", "value": "Jyv\u00e4skyl\u00e4n yliopisto", "language": "fi", "element": "contributor", "qualifier": "organization", "schema": "dc"}, {"key": "dc.contributor.organization", "value": "University of Jyv\u00e4skyl\u00e4", "language": "en", "element": "contributor", "qualifier": "organization", "schema": "dc"}, {"key": "dc.subject.discipline", "value": "Orgaaninen kemia", "language": "fi", "element": "subject", "qualifier": "discipline", "schema": "dc"}, {"key": "dc.subject.discipline", "value": "Organic Chemistry", "language": "en", "element": "subject", "qualifier": "discipline", "schema": "dc"}, {"key": "yvv.contractresearch.funding", "value": "0", "language": "", "element": "contractresearch", "qualifier": "funding", "schema": "yvv"}, {"key": "dc.type.coar", "value": "http://purl.org/coar/resource_type/c_bdcc", "language": null, "element": "type", "qualifier": "coar", "schema": "dc"}, {"key": "dc.rights.accesslevel", "value": "openAccess", "language": null, "element": "rights", "qualifier": "accesslevel", "schema": "dc"}, {"key": "dc.type.publication", "value": "masterThesis", "language": null, "element": "type", "qualifier": "publication", "schema": "dc"}, {"key": "dc.subject.oppiainekoodi", "value": "4035", "language": "", "element": "subject", "qualifier": "oppiainekoodi", "schema": "dc"}, {"key": "dc.subject.yso", "value": "orgaaninen kemia", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.subject.yso", "value": "synteesi", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.subject.yso", "value": "kemiallinen synteesi", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.subject.yso", "value": "reaktiot", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.subject.yso", "value": "valokemia", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.subject.yso", "value": "l\u00e4\u00e4keaineet", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.subject.yso", "value": "alkaloidit", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.subject.yso", "value": "alkeenit", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.subject.yso", "value": "organic chemistry", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.subject.yso", "value": "synthesis", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.subject.yso", "value": "chemical synthesis", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.subject.yso", "value": "reactions", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.subject.yso", "value": "photochemistry", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.subject.yso", "value": "medicinal substances", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.subject.yso", "value": "alkaloids", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.subject.yso", "value": "alkenes", "language": null, "element": "subject", "qualifier": "yso", "schema": "dc"}, {"key": "dc.rights.url", "value": "https://rightsstatements.org/page/InC/1.0/", "language": null, "element": "rights", "qualifier": "url", "schema": "dc"}]
|