Regiodivergent cascade cyclization/alkoxylation of allenamides via N-protecting group driven rearrangement to access indole and indoline derivatives

Abstract

A mild, palladium-catalyzed domino Heck-cyclization/alkoxylation sequence of aryl halide tethered allenamides is described, providing regiodivergent indole and indoline derivatives controlled by the N-protecting group. This room temperature reaction provided functionalizable...

Regio- and Stereoselective Hexafluoroisopropoxylation and Trifluoroethoxylation of Allenamides

“…Our group recently developed a Pd-catalyzed domino cyclization/alkoxylation of aryl halide tethered allenamides (1), producing regiodivergent indoles and indolines. 11 However, the alcohol scope was limited to methanol and ethanol. Surprisingly, a simple addition product 3a was observed when HFIP was employed as a solvent in our previous Pd-catalyzed conditions.…”

“…Our group recently developed a Pd-catalyzed domino cyclization/alkoxylation of aryl halide tethered allenamides ( 1 ), producing regiodivergent indoles and indolines . However, the alcohol scope was limited to methanol and ethanol.…”

Palladium-catalyzed cascade cyclization of allenamide with 2-iodoanilines to access functionalized indoloquinolines

“…On the basis of these preliminary results and previous reports, a plausible pathway is proposed (Scheme 3). 11 First, oxidative addition of Pd(0) to the C–I bond of allenamide 1a affords the palladium complex I . Then, intramolecular palladium insertion to the allene affords intermediate II , which can exist simultaneously with the resonance form of the π-allyl-Pd intermediate III .…”