Catalyst-Controlled Divergent Reactions of 2,3-Disubstituted Indoles with Propargylic Alcohols: Synthesis of 3<i>H</i>-Benzo[<i>b</i>]azepines and Axially Chiral Tetrasubstituted Allenes

Abstract

Catalyst-controlled divergent reactions of 2,3-disubstituted indoles with propargylic alcohols were developed for the first time. In the presence of TsOH or B(C6F5)3 as catalyst, 2,3-disubstituted indoles reacted smoothly with 3-alkynyl-3-hydroxyisoindolinones to afford 3H-benzo[b]azepines by selective C2(sp2)–C3(sp2) ring expansion of indoles. In contrast, decreasing the catalyst strength (e.g., with chiral phosphoric acid) interrupted the cascade reactions, affording axially chiral tetrasubstituted allenes bearing an adjacent chiral quaternary carbon stereocenter. Control experiments provided insights into the reaction mechanism.