ChemInform Abstract: Synthetic Studies of cis-3a-Aryloctahydroindole Derivatives by Copper-Catalyzed Cyclization of N-Allyltrichloroacetamides: Facile Construction of Benzylic Quaternary Carbons by Carbon-Carbon Bond-Forming Reactions.

Abstract

Cyclization of N-(2-aryl-2-cyclohexen-1-yl)trichloroacetamides by a copper catalyst was investigated. It is crucially important for successful cyclization under mild conditions that alkoxycarbonyl groups are introduced to the nitrogen atom of the N-allyltrichloroacetamides as well as that CuCl(bipyridine) is used as the catalyst. Three compounds, N-(2-phenyl-2-cyclohexen-1-yl)-, N-[2-(3,4-dimethoxyphenyl)-2-cyclohexen-1-yl]-, and N-[2-(3,4-methylenedioxyphenyl)-2-cyclohexen-1-yl]trichloroacetamides, where the Cbz or MeO2C− group was attached to the nitrogen atom, were instantly converted to the corresponding trichlorinated cis-3a-aryloctahydroindol-2-ones in high yields at room temperature. The reactions offer a facile access to alkaloid skeletons such as mesembrines and crinines; as the simplest examples, total synthesis of (±)-mesembrane and (±)-crinane was accomplished. The effect of alkoxycarbonyl substituents in the amide group was compared with that of the methyl substituent. N-Methyl-N-(2-phenyl-2-...