Enantioselective Dearomatization of Indoles by an Azoalkene-Enabled (3+2) Reaction: Access to Pyrroloindolines.

The enantioselective dearomatization of indoles by an organocatalytic (3+2) reaction has been established. The reaction makes use of simple indole derivatives as substrates, and employs azoalkenes reaction partners. A wide range of pyrroloindolines containing an all-carbon quaternary stereogenic center were readily prepared in high yields and with excellent enantioselectivities.

Enantioselective synthesis of mixed 3,3'-bisindoles via a phosphine-catalyzed umpolung γ-addition of 3'-indolyl-3-oxindoles to allenoates.

An enantioselective umpolung γ-addition reaction of 3'-indolyl-3-oxindoles to allenoates catalyzed by amino acid-derived bifunctional phosphine catalysts has been developed. A wide range of chiral mixed 3,3'-bisindole scaffolds containing an all-carbon quaternary stereogenic center were obtained in high yields and with excellent enantioselectivities. 3,3'-Bisindoles are valuable synthetic intermediates, the employment of which led to formal total syntheses of (+)-Chimonanthine, (+)-Folicanthine and (-)-Calycanthine, as well as facile creation of useful pyrrolidinoindoline core structure.