Abstract: | A directed cyclization‐dehydration cascade of α‐aryloxy ketones and α‐arylamino ketones was efficiently catalyzed by a cationic iridium‐BINAP complex, which afforded various types of 4‐substituted benzofurans and indoles in high yields with complete regioselectivity. The newly developed protocol also enabled the enantioselective preparation of chiral 4‐acetyloxindole using a chiral iridium catalyst. |