Steric compression inhibition

Steric Compression Inhibition of [2+2] Photocycloaddition. Following the pioneering work of Schmidt and co-workers on the solid state photodimerization reactions of the cinnamic acids... 

A bulky substituent close to the reaction centre may increase the non-bonded compression energy as the transition state is formed this will cause an increase in A//. It will also hinder the close approach of solvent molecules to the reaction centre, thus reducing the maximum amount of stabilization possible (steric inhibition of solvation). This will result in a further increase in AH, but since decreased solvation means less ordering of solvent molecules about the transition state, there is a compensating increase in AS. Another effect of the bulky substituent may be to block certain vibrational and rotational degrees of freedom more in the (more crowded) transition state than in the initial state, and so to reduce AS. These are the most important of the simple effects of a bulky substituent and can be used to explain most of the relationships of Table 25. 

The data for acid-catalyzed ester formation in cyclohexanol are doubly interesting. The activation parameters are closely similar to those for the acid-catalyzed hydrolysis of the corresponding ethyl esters. The enthalpy of activation is considerably higher than for esterification in methanol this is probably a result of steric inhibition of solvation, as well as non-bonded compression in the transition state, as suggested by the entropies of activation, which are also significantly higher than with methanol, especially for compounds without ortho substituents which presumably have more transition state solvation to lose. 

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