This review examines some typical examples that illustrate the significant developments reported recently, in which external chiral ligands have been used as asymmetric controllers in stoichiometric and catalytic amounts. 1 . Introduction 2. Carbon-Carbon Bond Formation 2.1. Addition of Organometals to Aldehydes and Ketones 2.2. Addition of Organometals to α,β-Unsaturated Carbonyl Compounds 2.3. Alkylation of Enolates 2.4. Diels-Alder Reaction 2.5. Others 3. Deprotonation Using Chiral Lithium Amides 4. Oxidation 4.1. Epoxidation 4.2. Dihydroxylation 5. Reduction 6. Others 7. Conclusion