Water Modulated Diastereoselective Synthesis of cis/trans-Spiro[indoline-3,6'-naphtho[2,3-c]carbazoles].

p-TsOH catalyzed Diels-Alder reaction of 2-(1-alkylindol-3-yl)naphthalene-1,4-diones and 3-phenacylideneoxindoles showed fascinating diastereoselectivity. The reaction with the hydrated p-TsOH afforded trans-isomers of dihydrospiro[indoline-3,6'-naphtho[2,3-c]carbazoles] as major products. Alternatively, the reaction with anhydrous p-TsOH under a Dean and Stark apparatus predominately gave cis-isomer of dihydrospiro[indoline-3,6'-naphtho[2,3-c]carbazoles]. On the other hand, the similar p-TsOH catalyzed reaction of 2-(indol-3-yl)naphthalene-1,4-diones with 3-arylideneindolin-2-ones afforded cis/trans-isomers of dihydrospiro[indoline-3,6'-naphtho[2,3-c]carbazoles]. Additionally, the p-TsOH catalyzed reaction of 2-(indol-3-yl)naphthalene-1,4-diones with 2-arylidene-1,3-indanediones gave the expected spiro[indene-2,6'-naphtho[2,3-c]carbazoles] in satisfactory yields.