Preparation of chiral [2]paracyclo(5,8)quinolinophane - based cinchonoid analogue organocatalysts for stereoselective syntheses

master's thesis

• Title (croatian): Priprava kiralnih derivata cinhonidina na [2]paraciklo(5,8)kinolinofanu kao organokatalizatora u stereoselektivnim sintezama
• Author: Silvija Petković
• Mentor: Svjetlana Krištafor (mentor)
• Committee member: Svjetlana Krištafor (predsjednik povjerenstva)
• Committee member: Lidija Furač (član povjerenstva)
• Committee member: Nataša Perin (član povjerenstva)
• Granter: University of Zagreb; Faculty of Chemical Engineering and Technology; Zagreb
• Defense date and country: 2015-07-13, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry; Applied Chemistry

Abstract

The aim of this thesis was to synthesize chiral cinchonoid analogues, [2](5,8)quinolinophane and quinoline organocatalysts that could be used in stereoselective syntheses. The presence of the quinoline system makes the molecule of quinolinophane a great "building block" for the synthesis of chiral cinchona analogues as potential organocatalysts. In other words, it would be sufficient to introduce into the molecule a tertiary amino group and a chiral carbon bounded to a hydroxyl group to obtain a molecule that has all the elements of chirality as the natural cinchonoids. The only difference lies in the fact that a central chirality associated with quinuclidine ring of cinchonoids is replaced by the planar chirality associated with the system "quinolinophane". In addition, the quinolinophane constitutes a chiral "building block" of extreme versatility. In fact, through simple transformations, it is possible to obtain different structural combinations in which the determined elements for the asymmetric induction (the tertiary amino group, the hydroxylated chiral carbon and the planar chirality system) can be differently assembled.
With that in mind, the scope was to determine contribution of planar and central chirality of (R)-[2]paracyclo[2](5,8)quinolinophane derivatives exhibiting both type of chirality to the asymmetric induction (Figure 1). For sake of comparison envisaged was to prepare also some chiral (S)- and (R)-trifluoromethylsulfoxyamide derived from 4-bromoquinoline.

Abstract (croatian)

Cilj ovog rada bio je sintetizirati kiralne analoge cinhonoidina, [2]paraciklo(5,8)kinolinofane i kinolinske organokatalizatore koji bi se mogli koristiti u stereoselektivnim sintezama. Zbog prisutnosti kinolinskog sustava molekula kinolinofana je izvrstan building block za sintezu kiralnih cinchona analoga kao potencijalnih organokatalizatora. Drugim riječima, dovoljno je uvesti u molekulu tercijarnu amino skupinu i kiralni ugljik vezan na hidroksilnu skupinu, čime se dobije molekula koja ima sve elemente kiralnosti kao prirodni cinchonoidi. Jedina razlika je u tome što je centralna kiralnost povezana s kinuklidinskim prstenom cinchonoida zamjenjena planarnom kiralnošću kinolinofanskog sustava. Nadalje, kinolinofan predstavlja kiralni building block izuzetne raznovrsnosti. U stvari, jednostavnim transformacijama moguće je dobiti različite strukturne kombinacije u kojoj su utvrđeni elementi za asimetričnu indukciju (tercijarna amino skupina, hidroksilirani kiralni ugljik, planarni kiralni sustav).
Imajući to na umu, opseg je utvrditi doprinos planarne i središnje kiralnosti (R)-[2]paraciklo[2](5,8)kinolinofanskih derivata koji pokazuju oba tipa kiralnosti u asimetričnoj indukciji (Slika 1). Radi usporedbe pripremljeni su i kiralni (S)- i (R)-trifluorometilsulfoksiamidi izvedeni iz 4-bromkinolina.

• Keywords: organocatalysis; cinchona analogues; asymmetric induction; chirality
• Keywords (croatian): organokataliza; cinchona analozi; asimetrična indukcija; kiralnost
• Language: english
• URN:NBN: urn:nbn:hr:149:871764
• Study programme: Title: Applied Chemistry - Graduate study; specializations in: Environmental chemistry and green technologies, Advanced materials and technologies, Applied organic chemistry; Course: Applied organic chemistry; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra primijenjene kemije (magistar/magistra primijenjene kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access
• Repository: Repository of Faculty of Chemical Engineering and Technology University of Zagreb
• Created on: 2016-12-09 12:18:55