Original title: Syntéza, štěpení, vlastnosti a aplikace azahelicenů
Translated title: On Azahelicenes: Synthesis, Resolution, Properties and Applications
Authors: Míšek, Jiří ; Starý, Ivo (advisor) ; Kroutil, Jiří (referee) ; Macháček, Vladimír (referee) ; Závada, Jiří (referee)
Document type: Doctoral theses
Year: 2008
Language: eng
Abstract: [eng] [cze]
1 Abstract A novel and modular approach to azahelicenes has been developed. Using 12+2+2) cyclotrimerisation of appropriate triyne as a key step, azahelicenes 83, 84 and 85 have been prepared (Scheme 1). &83 84 Scheme 1. Aza[6]he|icenes 84 and 85 have shown to be sufÍicienl|y conÍigurationa||y stable and have been resolve inlo individual enantiomers by the diastereoisomeric sa|t crysta|isation and chira| HPLC. This a||owed to determine exact Va|ues oÍ racemisation barriers Íorboth aza[6]he|icenes 84 and 85. In general' both hexacyclic derivatives 84 and 85 are stable enough to be used in asymmetric transÍormations or chira| sensing. The abi|ity oÍ aza[6]he|icenes 84 and 85 to serve as chira| ligands íortransition meta|s has been proven by the preparation and X. ray analysis ol corresponding si|ver comp|exes. lnteresting chira| selÍ.recogniton properties oÍaza[6]he|icenes 84 in gas phase have been described using mass spectrometry techniques. |n order to comp|ement inÍormation about azahelicenes basicilies, gas phase proton afÍinities oÍ derivatives 84 and 85 and so|ution phase dissociation constants oÍ azahe|icenes 83. 84 and 85 have been determined. Eventua||y, the Íirst uti|ization oÍ azahe|icene in asymmetric catalysis has been demonstrated by the successÍu| use oÍ optical|y pure aza[6]he|icene... t 8 Shrnutí o By|a Vyvinuta nová, modulární strategie pro přípravu azahe|icenů 83, 84 a 85. . Hexacyklické deriváty 84 a 85 byly poprvé rozštěpeny na jednot|ivé enantiomery a jejich abso|utní konÍigurace by|a přiřazena. . By|y určenyracemizačníbariéry aza[6]he|icenů 84 a 85 a by| popsán vztah mezi strukturou aza[6]helicenů 84 a 85 a ve|ikostí racemizačníbariéry. . By|a prokázána schopnost aza[6]he|icenů 84 a 85 tvořit komp|exy s přechodnými kovy' o By|y popsána V|astnost azahe|icenů tvořit homochirá|ní agregáty jak v p|ynné' tak v pevné Íázi. . By|y určeny bazicity azahe|icenů v p|ynné Íázi a v roztoku. . Bylo popsáno první vyuŽití azahe|icenů v enantiose|ektivní kata|ýze. 19

Institution: Charles University Faculties (theses) (web)
Document availability information: Available in the Charles University Digital Repository.
Original record: http://hdl.handle.net/20.500.11956/5535

Permalink: http://www.nusl.cz/ntk/nusl-274199


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Universities and colleges > Public universities > Charles University > Charles University Faculties (theses)
Academic theses (ETDs) > Doctoral theses