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The electrophilic amination constitutes an unconventional C−N bond‐forming reaction. Asymmetric versions have been developed using chiral reagents or catalysts and starting from optically pure substrates. The aminated products can be obtained with high stereoselectivities. These methodologies are flexible routes for the synthesis of α‐amino acids and nitrogen heterocycles. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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