Home > General > Chirale mono- und bedentate Phosphorliganden fur die enantioselektive Metallkatalysierte Hydrierung
Chirale mono- und bedentate Phosphorliganden fur die enantioselektive Metallkatalysierte Hydrierung

Chirale mono- und bedentate Phosphorliganden fur die enantioselektive Metallkatalysierte Hydrierung

          
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About the Book

Im Rahmen dieser Arbeit wurden neuartige Liganden fur die Metall-katalysierte enantioselektive Hydrierung von Olefinen, Iminen und Acetophenon entwickelt. Im ersten Teil wurden fur die Rhodium-katalysierte asymmetrische Hydrierung von funktionalisierten Olefinen zunachst neutrale und anionische monodentate Phosphorliganden dargestellt. Im Gegensatz zu den neutralen Phosphorliganden weisen die anionischen Systeme eine negative Ladung auf ihrem Boratrest auf. Hinsichtlich der asymmetrischen Induktion sind diese anionischen monodentaten Liganden oftmals effizienter als ihre neutralen Analoga. Mit monodentaten chiralen Phosphorliganden konnten sehr gute Enantioselektivitaten von bis zu 99 % ee realisiert werden. Des Weiteren wurden auch Ligandenmischungen bestehend aus zwei verschiedenen monodentaten Liganden getestet. NMR-Untersuchungen zeigten, dass durch die Verwendung eines anionischen und eines neutralen Liganden der Anteil der Heterokombination auf Kosten der beiden Homokombinationen erhoht werden kann. In den meisten Fallen fuhrte der Einsatz von solch einer Mischung im Vergleich zu zwei ungeladenen Liganden zu einer weiteren Steigerung der Aktivitat und bzw. oder der Selektivitat. Durch die Wahl des geeigneten monodentaten Koordinationspartners wurde der Anteil des Heterokomplexes weiter gesteigert. Als besonders effizienter Partner erwiesen sich hierbei die Diolester der Phosphonsaure. Diese Systeme ergaben auf Grund von sekundaren Wechselwirkungen in einigen Fallen einen quantitativen Anteil der Heterokombination. Mit solchen Sytemen konnte der Enantiomerenuberschuss gegenuber der entsprechenden Homokombination teilweise von 76 % auf bis zu 97 % gesteigert werden. Im zweiten Teil dieser Arbeit wurden sekundare Phosphinoxide (SPO) sowohl als P,P- als auch als P,N-Liganden fur die Iridium-katalysierte Hydrierung von Iminen untersucht. Dabei zeigten insbesondere SPO-Liganden mit einem Ferrocengrundgerust vielversprechende Resultate mit bis zu 95 % ee. In der Kupfer-katalysierten Hydrierung von Acetophenon erwiesen sich Liganden, die einen großeren Chelatring mit den Metallkatalysatoren bilden, als geeignet. Daher wurden Xanthen basierte P,P- und P,N-SPO-Systeme entwickelt und zusatzlich mit einem Phosphinoxazolin analogen Liganden mit Xanthengrundgerust erganzt. Diese Xanthenliganden wurden in der Hydrierung von Olefinen und Acetophenon mit verschiedenen Metallen getestet. Sie erwiesen sich jedoch bisher nicht als erfolgreiche Liganden fur die Metall-katalysierte Hydrierung.


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Product Details
  • ISBN-13: 9783869559445
  • Binding: Paperback
  • Language: German
  • Width: 343 mm
  • ISBN-10: 3869559446
  • Height: 210 mm
  • Weight: 13 gr

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