Synthesis of Annulated Indolines by Reductive Fischer Indolization.

Cyclic ß-oxoesters and arylhydrazine derivatives were converted at ambient temperature under modified Fischer indolization conditions to furnish annulated indolines with quaternary bridgehead carbon center. Reaction conditions were Brønsted acidic (with CF3 CO2 H), but also reductive (with Et3 SiH). The latter reduced intermediate iminium ions under formation of the 2,3-dihydroindole product constitutions. Racemic products (13 examples) were obtained as single diastereoisomers with relative cis-configuration, which was proved in two cases by single-crystal X-ray structure analysis. Conversion of 4-bromo-1-indanone-2-carboxylate and 4-bromophenylhydrazine gave indeno[1,2-b]indolines with either 1-bromo, 8-bromo, or 1,8-dibromo substitution, which were further diversified by Suzuki coupling reactions with several arylboronic acids (nine examples).