Base-Mediated Cyclopentannulation of Ynones with Amino Crotonates for Regio- and Stereoselective Synthesis of Pentafulvenes and Cyclopenta[c]quinolines

A regio- and stereoselective synthesis of unsymmetrically substituted pentafulvenes is reported via the condensation of readily available ynones and amino crotonates under very mild conditions. The mechanism of this 3 + 2 annulation involved a vinylogous Michael addition followed by an intramolecular enamine aldol condensation. Substrates with o-bromo tether further cyclized to pentannulated hydroquinolines through an isomerization/SNAr in the same reaction pot at the elevated temperature.