Neighboring Hydroxyl Group-Assisted Allylboration and Lewis Acid-Mediated Carbonyl-Ene Reaction for Access to a Hapalindole Cyclohexane Core with Multiple Contiguous Stereogenic Centers.

A neighboring hydroxyl group-assisted allylboration of 3-indolyl ketones with γ,γ-disubstituted allylboronic acids is reported, affording various 3-indolyl-substituted homoallylic alcohols in good yields with excellent diastereoselectivies (up to >20:1 dr). The hydroxyl group not only played a vital role in the challenging allylboration but was elaborated for the subsequent construction of a hapalindole cyclohexane core by a highly diastereoselective Lewis acid-catalyzed carbonyl-ene reaction. In the overall process, four contiguous stereogenic centers including two quaternary stereogenic centers were installed.