NEW CLASSES OF TRANSITION METAL N-HETEROCYCLIC CARBON(0) CATALYSTS FOR C–C AND C–N BOND FORMING REACTIONS Public Deposited

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  • March 20, 2019
Creator
  • Roberts, Courtney
    • Affiliation: College of Arts and Sciences, Department of Chemistry
Abstract
  • I. Development of Carbodicarbene-Rh Complexes The development and synthesis of new carbodicarbene-Rh(I) pincer complexes is reported. These complexes incorporate electron-rich carbon(0) ligands and represent the first carbodicarbene pincer complexes ever reported. II. Carbodicarbene-Rh Catalyzed Hydroamination of Dienes The first example of carbodicarbene ligands used in catalysis is reported. The hydroamination of 1,3-dienes is catalyzed by 1-5 mol% of readily available carbodicarbene-Rh catalysts to generate a variety of allylic amines in up to 97% yield. III. Lewis Acid Activation of Carbodicarbene-Rh Catalysts for Hydroarylation of Dienes The use of Lewis acid cocatalysts to activate carbodicarbene-Rh complexes for the hydroarylation of 1,3-dienes is reported. Substituted indoles and pyrroles are competent reaction partners with both terminal and internal 1,3-dienes. NMR spectroscopy is used to study the effect of the Lewis acid on the carbodicarbene-Rh complexes. IV. Development of Chiral Carbodicarbene and Cyclic Bent Allene Catalysts for Enantioselective Hydrofunctionalization The development and synthesis of chiral carbodicarbene and cyclic bent allene Rh(I) complexes is reported. Using these catalysts, enantioselective hydroarylation, hydroamination, hydroalkylation, and hydroallylation is enabled in yields of up to 80% and enantioselectivities of up to 85%.
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Rights statement
  • In Copyright
Advisor
  • Alexanian, Erik
  • Miller, Alexander
  • Dempsey, Jillian
  • Meek, Simon
  • Waters, Marcey
Degree
  • Doctor of Philosophy
Degree granting institution
  • University of North Carolina at Chapel Hill Graduate School
Graduation year
  • 2016
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