Summary
Nitrile (C≡N bond) activation for direct organic synthesis has been less explored so far due to a high redox potential of nitrile and its low dissociation energy of C−CN bond. Herein, we demonstrate a direct reductive coupling of nitriles and 1,2-phenylenediamines to yield various benzimidazoles in excellent yields (95%–99%) by using rhodium phosphide (Rh
2
P) catalyst supported on lignin-derived carbon (LC) using H
2
(or hydrazine hydrate) as a hydrogen source. The high catalytic performance of Rh
2
P/LC is attributed to enhanced charge transfer to Rh and strong P−Rh interactions. Our isotope trace experiment confirms the presence of H/D exchange between H
2
and the inert –CD
3
group of CD
3
CN
via
an intramolecular D-shift. Reusability of Rh
2
P/LC is further demonstrated by a seven-time recycling without evident loss of activity. This research thus highlights a great potential in organic transformation with nitrile as a synthetic building block.
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