Ynone Promoted Deaminative Coupling of Gramines with <i>C</i>- and <i>N</i>-Nucleophiles

The deaminative coupling of gramines with nucleophiles represents a versatile approach for structure diversification, but often involves non innocent conditions and/or reagents. Here a new acetylenic reagent <b>2</b> is developed for the C-N bond activation of gramines and their in situ coupling with <i>C</i>- and <i>N</i>-centered nucleophiles. Using the new acid/base- and redox-neutral ynone reagent <b>2</b> the coupling reactions proceed exceedingly as exemplified by the synthesis of several indol-3-ylmethyl derivatives, including new indole-benzodiazepine and indole-hydrazone conjugates.