Nucleophilic epoxidation is the formation of epoxides from electron-deficient double bonds through the action of nucleophilic oxidants. Nucleophilic epoxidation methods represent a viable alternative to electrophilic methods, many of which do not epoxidize electron-poor double bonds efficiently. Although the most commonly used asymmetric epoxidation methods (the Sharpless-Katsuki, and Jacobsen epoxidations) rely on the catalytic reactivity of electrophilic oxidants, nucleophilic oxygen sources substituted with a suitable leaving group can also act as epoxidation reagents. The classic example, the Weitz-Scheffer reaction employs hydrogen peroxide under basic conditions (Z = OH below). Other notable examples have employed hypochlorites (Z = Cl) and chiral peroxides (Z = OR*). (1) Asymmetric versions of the above reaction have taken advantage of a number of strategies for achieving asymmetric induction. The highest yielding and most enantioselective methods include: Use of stoichiometric chiral oxidant Use of stoichiometric metal peroxides substituted with chiral ligands Use of stoichiometric chiral base Use of polypeptides Although the mechanisms of each of these reactions differ somewhat, in each case the chiral catalyst or reagent must be involved in the enantio determining conjugate addition step. Cis-epoxides are difficult to access using nucleophilic epoxidation methods. Nearly all nucleophilic epoxidations of cis olefins afford trans epoxides. Mechanism and Stereochemistry Prevailing Mechanism The mechanism of nucleophilic epoxidation begins with conjugate addition of the peroxide (or other O-nucleophilic species) to the enone. Metal ions or conjugate acids present in solution coordinate both the peroxide oxygen and the enolate oxygen. Attack of the enolate on the peroxide oxygen generates the epoxide product and releases a leaving group. (2) Because the process is stepwise, the configuration of the carbon-carbon double bond is not necessarily preserved. Both cis and trans enones form trans epoxides under nearly all nucleophilic epoxidation conditions (methods employing lanthanide-BINOL systems are the exception). Stereoselective Variants How stereoselectivity is achieved in asymmetric nucleophilic epoxidations depends on the method employed. Covered here are various methods for the asymmetric nucleophilic epoxidation of electron-poor olefins. See below for a survey of the substrate scope of the reaction. When chiral, non-racemic peroxides are used, the two transition states of epoxidation leading to enantiomeric products are diastereomeric. Steric interactions between the peroxide, enone, and templating cation M+ influence the sense of selectivity observed. (3) Methods that employ metal peroxides modified by chiral, non-racemic ligands operate by a similar mechanism in which the metal cation plays a templating role. Chiral zinc alkoxides under an