Carbazoaniline: Enantioselektive Kreuz-dehydrogenative Aminierungsreaktionen für die Darstellung asymmetrischer chiraler Diamine und ihre Anwendung als enantiomerenreinen Liganden

• Antragsteller: Professor Dr. Frederic W. Patureau
• Fachliche Zuordnung: Organische Molekülchemie - Synthese, Charakterisierung
• Förderung: Förderung von 2014 bis 2018
• Projektkennung: Deutsche Forschungsgemeinschaft (DFG) - Projektnummer 257130133

• Erstellungsjahr: 2018

Zusammenfassung der Projektergebnisse

In conclusion, the project was in large part devoted to the exploration of the redox reactivity of phenothiazines (PTZs) and derivatives, in particular in metal-free cross dehydrogenative coupling reactions with phenols and indoles. Indeed, a notable serendipitous discovery at the beginning of project, led us to explore this reactivity. Although we deviated considerably from our original project objectives, we are nevertheless now closer to reaching the main objective than before (enantioselective C-N bond forming coupling reactions with H-bonded axial chirality). Indeed, many of the herein coupling methods operate now at more moderate temperatures, some at only 40 °C, and the vast majority of the new C-N coupled products are C-N chiral in the case of unsymmetrically substituted phenothiazine starting materials. Indeed, in most cases, a strong intramolecular O-H•••N Hydrogen-bond is evidenced by IR and X-ray. These objectives remain therefore on our list of realistic future goals.

Projektbezogene Publikationen (Auswahl)

• O2-mediated dehydrogenative amination of phenols. Angew. Chem. Int. Ed. 2015, 54, 4102
  M.-L. Louillat-Habermeyer, R. Jin & F. W. Patureau
  
• Mild, periodate mediated, dehydrogenative C-N bond formation with phenothiazines and phenols, Org. Lett. 2016, 18, 4491
  R. Jin, F. W. Patureau
  
• The cumene/O2 system: a very simple tool for the radical chain oxidation of some functional groups. N. J. Chem. 2017, 41, 6981
  A. Malekafzali, K. Malinovska, F. W. Patureau
  
• Mechanism of the Dehydrogenative Phenothiazination of Phenols. Chem. Eur. J. 2018, 24
  M. Goswami, A. Konkel, M. Rahimi, M.-L. Louillat-Habermeyer, H. Kelm, R. Jin, B. de Bruin, F. W. Patureau
  
• Phenothiazinimides: atom-efficient electrophilic amination reagents. Org. Lett., 2018, 20, 2884
  R. Jin, C. L. Bub, F. W. Patureau
  
• The strong Beta-CF3 shielding effect in HFIP and 100 other organic solvents revisited with O NMR. ChemCatChem 2018, 10, 1547
  A. Bernhardt, H. Kelm, F. W. Patureau