An unexpected route to hitherto unknown amidine-functionalized phosphinines has been developed that is rapid and simple. Starting from primary amines and CF3-substituted λ3,σ2-phosphinines, a cascade of dehydrofluorination reactions leads selectively to ortho-amidinephosphinines. DFT calculations reveal that this unusual transformation can take place via a series of nucleophilic attacks at the electrophilic, low-coordinate phosphorus atom.
N. T. Coles, L. J. Groth, L. Dettling, D. S. Frost, M. Rigo, S. E. Neale and C. Müller, Chem. Commun., 2022, 58, 13580 DOI: 10.1039/D2CC05178H
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