Base-promoted epoxide isomerization is the conversion of alkyl epoxides to ring-opened products through the action of strong base. Isomerizations of this type are most often used to synthesize allylic alcohols, although other products are possible. Introduction In the presence of lithium or aluminum amide bases, epoxides may open to give the corresponding allylic alcohols. Removal of a proton adjacent to the epoxide, elimination, and neutralization of the resulting alkoxide lead to synthetically useful allylic alcohol products. In reactions of chiral, non-racemic epoxides, the configuration of the allylic alcohol product matches that of the epoxide substrate at the carbon whose C–O bond does not break (the starred carbon below). Besides β-elimination some other reactions are possible, as metalation of the epoxide ring can take place competitively. Vinylogous eliminations are possible when the epoxide substrate is substituted with vinyl or dienyl groups. Unconstrained systems tend to form trans double bonds, as significant non-bonding interactions are avoided in the transition state for the formation of trans products (see equation (2) below). The strongly basic conditions required for most isomerizations of this type represent the reaction's primary disadvantage. (1) Mechanism and stereochemistry Prevailing mechanism Isomerization of epoxides to allylic alcohols under strongly basic conditions proceeds by a β-elimination process. A model has been advanced that invokes an initial complex between the lithium amide base and epoxide. Concerted C–O bond cleavage and deprotonation proceeds via a syn transition state to give an allylic alkoxide, which is protonated upon workup. Deprotonation typically occurs at the exist in the transition state for cis double bond formation. (2) Other processes may take place competitively under basic conditions, particularly when β-elimination is slow or not possible. These pathways likely begin with lithiation of a carbon in the epoxide ring, followed by α-elimination to afford a carbene intermediate. 1,2-hydrogen migration leads to ketones, while intramolecular C–H insertion affords cyclic alcohols with the formation of a new carbon-carbon bond.(3) In many cases when hexamethylphosphoramide (HMPA) is used as an additive with lithium amide bases, selectivity for the formation of allylic alcohols increases. These reactions are believed to proceed through E2 elimination. Stereoselective variants Chiral amide bases may be used in catalytic amounts to isomerize meso epoxides to chiral allylic alcohols with high enantioselectivity. (4) Scope and limitations Terminal epoxides suffer from the limitation that competitive nucleophilic addition of the base to the unsubstituted epoxide carbon may take place. Non-nucleophilic, sterically hindered