Advanced

Bicyclic Ligands and Catalysts in Asymmetric Synthesis

Friberg, Annika LU (2006)
Abstract (Swedish)
Popular Abstract in Swedish

Asymmetrisk katalys är ett omfattande forskningsområde där ett flertal olika typer av enantioselektiva katalysatorer har utvecklats och använts i en mängd olika kemiska reaktioner med varierande resultat. Det finns ingen katalysator som fungerar lika väl i alla applikationer, utan resultaten varierar från fall till fall och för vissa typer av substrat behövs det därför alternativa lösningar för att erhålla önskad selektivitet. Ett sätt att uppnå detta är att framställa nya typer av katalysatorer.



En ligand utgörs av en organisk struktur som genom att binda till en metall kan fungera som en katalysator i en kemisk reaktion (metallorganisk katalys). Även små organiska molekyler... (More)
Popular Abstract in Swedish

Asymmetrisk katalys är ett omfattande forskningsområde där ett flertal olika typer av enantioselektiva katalysatorer har utvecklats och använts i en mängd olika kemiska reaktioner med varierande resultat. Det finns ingen katalysator som fungerar lika väl i alla applikationer, utan resultaten varierar från fall till fall och för vissa typer av substrat behövs det därför alternativa lösningar för att erhålla önskad selektivitet. Ett sätt att uppnå detta är att framställa nya typer av katalysatorer.



En ligand utgörs av en organisk struktur som genom att binda till en metall kan fungera som en katalysator i en kemisk reaktion (metallorganisk katalys). Även små organiska molekyler kan fungera som selektiva katalysatorer för detta ändamål, vilket kallas organokatalys.



En betydande del av arbetet som beskrivs i den här avhandlingen har bestått i själva syntesutvecklingen av ett flertal 1,3- och 1,4-dioler baserade på ett stelt bicyklo[2.2.2]oktanskelett. För att framställa 1,3-diolerna utvecklades både en förbättrad syntes av deras startmaterial såväl som en effektiv väg till målmolekylerna. För syntesen av 1,4-diolerna användes en genetiskt modifierad jäst för att erhålla optiskt aktivt material.



De bicykliska diolernas användbarhet som metallorganiska katalysatorer utforskades genom att de applicerades, i närvaro av titantetraisopropoxid, i två olika typer av reaktioner; asymmetrisk reduktion av ketoner med katekolboran och addition av dimetylfosfit till aldehyder.



Studien expanderades till att även inkludera föreningar baserade på ett dibensobicyklo[3.3.1]nonanskelett, vilka användes som organokatalysatorer i en hetero-Diels-Alder reaktion. En av de dibensobicyklo[3.3.1]nonan baserade strukturerna, en diamin, användes även till att syntetisera kirala selektorer, av vilka två stationära faser tillverkades och utvärderades kromatografiskt med HPLC. (Less)
Abstract
Synthesis of compounds based on the structurally rigid bicyclo[2.2.2]octane and the dibenzobicyclo[3.3.1]nonane frameworks and also their application as ligands and catalysts in asymmetric synthesis are described.



For the synthesis of 1,3-diols based on the bicyclo[2.2.2]octane framework, an improved synthesis of the starting material bicyclo[2.2.2]octan-2,6-dione was developed and performed at 0.5 kg scale, as well as an effective synthetic route to the target diols.



A genetically engineered Saccharomyces cerevisiae strain was used for the preparation of key intermediates for the synthesis of 1,4-diols based on the bicyclo[2.2.2]octane framework. The 1,3- and 1,4-diols, together with Ti(OiPr)4, were... (More)
Synthesis of compounds based on the structurally rigid bicyclo[2.2.2]octane and the dibenzobicyclo[3.3.1]nonane frameworks and also their application as ligands and catalysts in asymmetric synthesis are described.



For the synthesis of 1,3-diols based on the bicyclo[2.2.2]octane framework, an improved synthesis of the starting material bicyclo[2.2.2]octan-2,6-dione was developed and performed at 0.5 kg scale, as well as an effective synthetic route to the target diols.



A genetically engineered Saccharomyces cerevisiae strain was used for the preparation of key intermediates for the synthesis of 1,4-diols based on the bicyclo[2.2.2]octane framework. The 1,3- and 1,4-diols, together with Ti(OiPr)4, were tested as catalysts in the asymmetric reduction of acetophenone with catecholborane and in the asymmetric addition of dimethylphosphite to aldehydes.



Several chiral cleft molecules (diols, amino alcohols and diamines) based on the dibenzobicyclo[3.3.1]nonane framework were synthesized and applied as organocatalysts in an asymmetric hetero-Diels-Alder reaction.



A primary diamine based on the dibenzobicyclo[3.3.1]nonane framework was used as the rigid central part for the synthesis of two chiral selectors with different length of their achiral spacers. These selectors were used for the preparation of two new chiral stationary phases, which were evaluated by chromatography (HPLC). (Less)
Please use this url to cite or link to this publication:
author
supervisor
opponent
  • Professor Moberg, Kristina, KTH
organization
publishing date
type
Thesis
publication status
published
subject
keywords
Organisk kemi, Organic chemistry, dibenzobicyclo[3.3.1]nonane catecholborane, bicyclo[2.2.2]octane, Asymmetric catalysis, organocatalysis
pages
77 pages
publisher
Division of Organic Chemistry, Lund University
defense location
Kemicentrum, sal K:B
defense date
2006-10-06 10:30
ISBN
91-7422-127-2
language
English
LU publication?
yes
id
aafcf5b9-b55d-4d8b-ab2e-8b4e46455072 (old id 547217)
date added to LUP
2007-10-13 10:52:12
date last changed
2016-10-27 17:10:55
@phdthesis{aafcf5b9-b55d-4d8b-ab2e-8b4e46455072,
  abstract     = {Synthesis of compounds based on the structurally rigid bicyclo[2.2.2]octane and the dibenzobicyclo[3.3.1]nonane frameworks and also their application as ligands and catalysts in asymmetric synthesis are described.<br/><br>
<br/><br>
For the synthesis of 1,3-diols based on the bicyclo[2.2.2]octane framework, an improved synthesis of the starting material bicyclo[2.2.2]octan-2,6-dione was developed and performed at 0.5 kg scale, as well as an effective synthetic route to the target diols.<br/><br>
<br/><br>
A genetically engineered Saccharomyces cerevisiae strain was used for the preparation of key intermediates for the synthesis of 1,4-diols based on the bicyclo[2.2.2]octane framework. The 1,3- and 1,4-diols, together with Ti(OiPr)4, were tested as catalysts in the asymmetric reduction of acetophenone with catecholborane and in the asymmetric addition of dimethylphosphite to aldehydes.<br/><br>
<br/><br>
Several chiral cleft molecules (diols, amino alcohols and diamines) based on the dibenzobicyclo[3.3.1]nonane framework were synthesized and applied as organocatalysts in an asymmetric hetero-Diels-Alder reaction.<br/><br>
<br/><br>
A primary diamine based on the dibenzobicyclo[3.3.1]nonane framework was used as the rigid central part for the synthesis of two chiral selectors with different length of their achiral spacers. These selectors were used for the preparation of two new chiral stationary phases, which were evaluated by chromatography (HPLC).},
  author       = {Friberg, Annika},
  isbn         = {91-7422-127-2},
  keyword      = {Organisk kemi,Organic chemistry,dibenzobicyclo[3.3.1]nonane catecholborane,bicyclo[2.2.2]octane,Asymmetric catalysis,organocatalysis},
  language     = {eng},
  pages        = {77},
  publisher    = {Division of Organic Chemistry, Lund University},
  school       = {Lund University},
  title        = {Bicyclic Ligands and Catalysts in Asymmetric Synthesis},
  year         = {2006},
}