Steric Effects on Reaction Rates. Part VIII. The Significance of Front Strain Release in Solvolysis of Bridgehead Derivatives

The steric requirements of leaving groups for 14 bridgehead derivatives have been examined using MM2 calculations. The strain varies almost monotonously throughout the series upon variation of the leaving group from H to C1, OH, CH₃, CH₃CH₂O, (CH₃)₃CO, (CH₃)₃C and no significant trends for differential F-strain effects are detected expect for the perhydrophenalene derivative 13 . The experimental rates of solvolysis of bridgehead derivatives correlate well with the calculated steric energy differences between substrate R-X and the corresponding carbenium ion R⊕. However, the strain calculations using the more recent force-fields ( MM2 ) disagree, in part, with those reported in the literature: chloride and p-toluenesulfonate leaving groups correlate with identical slopes, and the perhydrotriquinacene derivative 10 shows no anomalous behavior. The calculations suggest that F-strain and C,C-hyperconjugation should not play any dominant role in bridgehead solvolysis.