In the absence of hydrogen bonding, steric effects direct peroxide addition to the opposite face. However, perfluoric peracids are still able to hydrogen bond with protected alcohols and give normal selectivity with the hydrogen present on the peracid. Although the presence of an allylic alcohol does lead to increased stereoselectivity, the rates of these reactions are slower than systems lacking alcohols. However, the reaction rates of substrates with a hydrogen bonding group are still faster than the equivalent protected substrates. This observation is attributed to a balance of two factors. The first is the stabilization of the transition state as a result of the hydrogen bonding. The second is the electron-withdrawing nature of the oxygen, which draws electron density away from the alkene, lowering its reactivity. Acyclic allylic alcohols exhibit good selectivity as well. In these systems both A1,2 (steric interactions with vinyl) and A1,3 strain are considered. It has been shown that a dihedral angle of 120 best directs substrates which hydrogen bond with the directing group. This geometry allows for the peroxide to be properly positioned, as well as to allow minimal donation from the C-C pi into the C-O sigma star. This donation would lower the electron density of the alkene, and deactivate the reaction. However,vanadium complexes do not hydrogen bond with their substrates. Instead they coordinate with the alcohol. This means that a dihedral angle of 40 allows for ideal position of the peroxide sigma star orbital. In systems that hydrogen bond, A1,3 strain plays a larger role because the required geometry forces any allylic substituents to have severe A1,3 interactions, but avoids A1,2. This leads to syn addition of the resulting epoxide. In the vanadium case, the required geometry leads to severe A1,2 interactions, but avoids A1,3, leading to formation of the epoxide anti to the directing group. Vanadium catalyzed epoxidations have been shown to be very sensitive to the steric bulk of the vinyl group. Homoallylic alcohols are effective directing groups for epoxidations in both cyclic and acyclic systems for substrates which show hydrogen bonding. However these reactions tend to have lower levels of selectivity. While hydrogen bonding substrates give the same type of selectivity in allylic and homoallylic cases, the opposite is true of vanadium catalysts. A transition state proposed by Mihelich shows that for these reactions, the driving force for selectivity is minimizing A1,3 strain in a pseudo chair structure.