This review focuses on the application of glycol cleavage reactions in the synthesis and derivatization of complex natural products. Reagent classics as well as recent developments are discussed. 1Introduction 2Mechanistic Aspects 3Reagents and Examples 3.1Periodate and Hypervalent Iodine 3.1.1Periodic Acid and Periodates 3.1.2Periodate on Wet Silica Gel 3.1.3Phenyliodine Diacetate 3.1.4Other Iodine Reagents 3.2Lead Tetraacetate 3.3Chromium Reagents 3.3.1Pyridinium Chlorochromate 3.3.2Other Chromium Reagents 3.4Ruthenium Reagents 3.4.1Tetra-n-propylammonium Perruthenate 3.4.2Other Ruthenium Reagents 3.5Manganese Reagents 3.5.1Manganese(III) Acetate 3.5.2Manganese Dioxide 3.5.3Other Manganese Reagents 3.6Miscellaneous 4Conclusion