Phase-Transfer-Catalysed Synthesis of Pyrroloindolines and Pyridoindolines by a Hydrogen-Bond-Assisted Isocyanide Cyclization Cascade

摘要

A cascade reaction that generates pyrrolo- and pyridoindoline motifs from isocyanide precursors under phase-transfer conditions is described. This transformation proceeds at room temperature in the presence of a quaternary ammonium catalyst and base to generate functionalized products containing an all-carbon quaternary stereocentre. Quantum chemical calculations demonstrated that intramolecular general acid catalysis plays a key accelerating role through stabilization of developing charge in the transition state, and that the reaction is best described as a 5-endo dig cyclization, rather than an anionic 6p electrocyclization. Investigations employing chiral phase-transfer catalysts have given promising selectivities to date.