An Unexpected Inversion of Enantioselectivity in a Copper-Catalyzed Intramolecular­ Desymmetric Aryl C–N Coupling Reaction

Abstract

Enantioselective formation of indolines was achieved through desymmetrization of α,α-bis(2-iodobenzyl)glycines under the catalysis of copper(I) iodide and (2S,3aS,7aS)-octahydro-1H-­indole-2-carboxylic acid. An unexpected inversion of enantioselectivity was observed when achiral additives such as 4-(N,N-dimethylamino)pyridine were added which work together with the ligand. The configuration-reversed products were obtained in moderate yields as well as moderate ee values.

Key words

asymmetric desymmetrization - indolines - copper catalysis - N-arylation - inversion

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