Organic reactions involving α-amino alkoxides as intermediates are reviewed. Emphasis is placed on the author's work concerning the preparation and use of α-amino alkoxides as protective groups and metalation directors for directed lithiation reactions. 1. Introduction 2. An Alternative Preparation of α-Amino Alkoxides 3. Ortho Lithiation Directed by α-Amino Alkoxides 3.1 The Initial Studies 3.2 Rate Enhancement via Intramolecular TMEDA-Like Assisted Metalation 3.3 Low-Temperature Ortho Lithiation of Aryl α-Amino Alkoxides 3.4 Regioselective Lithiation Controlled by Varying the Amine Component of the α-Amino Alkoxide 4. Lithiation of Heterocycles Directed by α-Amino Alkoxides 4.1 Regioselective Ring Lithiation 4.2 N-Methyl Lithiation of N-Methylpyrroles 4.3 N-Methyl Lithiation of N-Methylindoles 4.4 Regioselective Substitution of Methoxypyridinecarboxaldehydes 5. Conclusions