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  • Title: Titanocene-Mediated Dinitrile Coupling: A Divergent Route to Nitrogen-Containing Polycyclic Aromatic Hydrocarbons.
    Author: Kiel GR, Samkian AE, Nicolay A, Witzke RJ, Tilley TD.
    Journal: J Am Chem Soc; 2018 Feb 21; 140(7):2450-2454. PubMed ID: 29383934.
    Abstract:
    A general synthetic strategy for the construction of large, nitrogen-containing polycyclic aromatic hydrocarbons (PAHs) is reported. The strategy involves two key steps: (1) a titanocene-mediated reductive cyclization of an oligo(dinitrile) precursor to form a PAH appended with di(aza)titanacyclopentadiene functionality; (2) a divergent titanocene transfer reaction, which allows final-step installation of one or more o-quinone, diazole, or pyrazine units into the PAH framework. The new methodology enables rational, late-stage control of HOMO and LUMO energy levels and thus photophysical and electrochemical properties, as revealed by UV/vis and fluorescence spectroscopy, cyclic voltammetry, and DFT calculations. More generally, this contribution presents the first productive use of di(aza)metallacyclopentadiene intermediates in organic synthesis, including the first formal [2 + 2 + 2] reaction to form a pyrazine ring.
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