Catalyst‐ and Substrate‐Controlled Regiodivergent Synthesis of Carbazoles through Gold‐Catalyzed Cyclizations of Indole‐Functionalized Alkynols

A wide variety of regioselectively substituted carbazole derivatives can be synthesized by the gold‐catalyzed cyclization of alkynols bearing an indol‐3‐yl and an additional group at the homopropargylic positions. The regioselectivity of the process can be controlled by both the oxidation state of the gold catalyst and the electronic nature of the substituents of the alkynol moiety. The 1,2‐alkyl migration in the spiroindoleninium intermediate, generated after indole attack to the activated alkyne, is favored with gold(I) complexes and for electron‐rich aromatic substituents at the homopropargylic position, whereas the 1,2‐alkenyl shift is preferred when using gold(III) salts and for alkyl or non‐electron‐rich aromatic groups. A gold‐catalyzed regiodivergent synthesis of carbazoles from alkynols bearing at the homopropargylic positions an indol‐3‐yl and an additional group has been described. The nature of R2 is crucial for the regiocontrol, promoting the 1,2‐alkyl migration with electron‐rich aromatics. In addition, whereas gold(III) salts favor the 1,2‐alkenyl shift, gold(I) complexes are more prone to promote 1,2‐alkyl migrations.