The C–N bond activation of N-heterocycle compounds has been widely investigated in both homogeneous and heterogeneous systems, and examples include the hydrodenitrogeneration (HDN) process in which N-hyterocycles present in petroleum or coal-based liquids are converted to NH3 and nitrogen-free hydrocarbons. To date, Wolczanski and Wigley reported reductive C–N bond cleavages of pyridine (or analogues) by low-valent Nb and Ta species, respectively. We have previously reported a ring-opening and denitrogeneration reaction of pyridine and picolines by a titanium (IV) alkylidyne [(PNP)Ti(≡CtBu)] with a robust PNP pincer ligand (PNP– = [N-(2-diisopropylphosphino-4-methylphenyl)2]–). To our knowledge, examples of C–N bond cleavage in fused N-heterocycles such as quinoline have not been reported in well-defined homogeneous systems. Herein, we report ring-opening reactions of quinoline and isoquinoline by a transient and low-valent titanium (II) alkyl complex. The mechanistic study of the ring-opening reactions by DFT calculation will also be discussed in this presentation.

Ring-opening reactions of quinoline and isoquinoline with a low-valent titanium alkyl complex

253rd National Meeting (2017)

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