Reaction centre accessibility. II. Role of reaction centre congestion in the calculation of reaction centre accessibility

Abstract Accessibility to reaction centres is as important as electronic reactivity in determining the success of a reaction. The possibility of its calculation becomes a necessary requisite in the prediction of reaction products. Using a recently proposed approach to the calculation of reaction centre congestion based on a two dimensional representation of molecules, a new system has been realised that can quickly evaluate the desired accessibility. The system is based on the simulation of the steric interaction between reactants in different orientations. The calculation of an interaction energy for each orientation and their combination permits the approximate estimation of the reaction probability for the steric factors concerned. Even though all the operations were performed using a two-dimensional representation the results are encouraging. It is obvious that at this level it is impossible to predict face accessibility preference.