Fluorescence spectroscopy of a naturally occurring carbazole alkaloid: murrayanine

The fluorescence properties of a naturally occurring carbazole alkaloid, murrayanine, have been studied in various polar solvents and micellar systems. It was found that fluorescence peak position and intensity are extremely sensitive to the nature of the solvent medium. Murrayanine fluorescence has been further utilized to determine the critical micellization concentration of Pluronic F68, an amphiphilic copolymer with potential applications in drug-delivery. Time-resolved fluorescence and fluorescence anisotropy decay of murrayanine measured in several n-alcohols display a monotonic retardation with increasing chain-lengths of the alcohols.     

Total Synthesis of Murrayanine Involving 4,5‐Dimethyleneoxazolidin‐2‐ones and a Palladium(0)‐Catalyzed Diaryl Insertion

A new total synthesis of the natural carbazole murrayanine ( 1 ) was developed by using the 4,5‐dimethyleneoxazolidin‐2‐one 12 as starting material. The latter underwent a highly regioselective Diels–Alder cycloaddition with acrylaldehyde (=prop‐2‐enal; 13 ) to give adduct 14 (Scheme 3). Conversion of this adduct into diarylamine derivative 9 was carried out via hydrolysis and methylation (Scheme 4). Differing from our previous synthesis, in which such a diarylamine derivative was transformed into 1 by a Pd^II‐stoichiometric cyclization, this new approach comprised an improved cyclization through a more efficient Pd⁰‐catalyzed intramolecular diaryl coupling which was applied to 9 , thus obtaining the natural carbazole 1 in a higher overall yield.