SN2 reactions with allylic substrates -: Trends in reactivity

The gas-phase identity S(N)2 reactions of allylic substrates has been studied by systematic altering of the nucleophile/nucleofuge X, the remote substituent Y, and the number of methyl substituents at the reaction centre: X- + YCHCHCZ(2)X -> YCHCHCZ(2)X + X- (X=H, CH3, NH2, F, Cl; Y=F, OH, H, CHO, BH2; Z = H, CHO. Key regions of the potential energy surfaces have been explored by MP2, B3LYP, G3B3 and G3 calculations; the latter two methods providing accurate estimates of the reaction barrier. The calculations show that irrespective of theoretical level, for the second row of the periodic table (X = CH3, NH2, OH, and F), the tendency is that the barrier height decreases in going from left to right in agreement with the previously observed trend for identity S(N)2 reactions at methyl. The barrier height decreases by introduction a pi electron withdrawing substituents, Y, remote from the reaction centre. The barrier height increases by introducing methyl groups (Z=CH3) next to the reaction centre, but the effect is less than half of that of changing the remote substituent from Y = CHO to Y = OH. The trends cannot be explained by simplified valence bond theory and are discussed in light of a simple electrostatic bonding model of the transition structure. (C) 2007 Elsevier B.V. All rights reserved.