Brønsted Acid-Catalyzed Dehydrative Nazarov-type Cyclization of CF3-Substituted 3-Indolylallyl Alcohols: Divergent Synthesis of 1-Trifluoromethylated Cyclopenta[b]indoles.

An expedient and efficient synthetic method for the divergent synthesis of 1-trifluoromethylated cyclopenta[b]indoles that relies on Brønsted acid-catalyzed dehydrative Nazarov-type cyclization of CF3-substituted 3-indolylallyl alcohols is described. Two classes of 1-trifluoromethylated cyclopenta[b]indoles can be easily accessed simply by changing the NH-protecting group of indoles. With arylsulfonyl protected 3-indolylallyl alcohols as starting materials, the reaction provided the arylsulfonyl protected 1-trifluoromethylated cyclopenta[b]indoles in good to excellent yields, whereas pivaloyl (Piv) protected substrates led to the formation of NH-free 1-trifluoromethylated cyclolopenta[b]indoles with another alkenyl isomer. This protocol features tunable chemoselectivity, operational simplicity, excellent functional group compatibility, and mild metal-free conditions.

Brønsted Acid-Catalyzed Dehydrative Nazarov-Type Cyclization/C2-N1 Cleavage Cascade of Perfluoroalkylated 3-Indolyl(2-benzothienyl)methanols.

A novel and unprecedented p-toluenesulfonic acid-catalyzed dehydrative Nazarov-type cyclization/C2-N1 bond cleavage cascade reaction of perfluoroalkylated 3-indolyl(2-benzothienyl)methanols has been developed. This reaction provides an efficient and practical protocol for the construction of highly functionalized benzothiophene-fused cyclopentenones with exclusive stereoselectivity. In addition, this cascade transformation also delineates a rare example of the involvement of the selective C2-N1 bond cleavage of indoles.