Entropy‐Driven Diastereoselectivity Improvement in the Paternò–Büchi Reaction of 1‐Naphthyl Aryl Ethenes with a Chiral Cyanobenzoate through Remote Alkylation

The precise stereocontrol of photocycloaddition reactions is still a significant challenge owing to their mechanistic complexity and the involvement of highly reactive and short‐lived intermediates. Attempts have hitherto been made through structural modifications, mostly by introducing steric conflicts, to increase the difference between the enthalpic barriers. Herein, we show that entropy plays a crucial role in influencing the diastereoselectivity of a Paternò–Büchi reaction. Remote meta alkylation of the donor caused nominal changes in its photophysical properties as well as those of the exciplexes derived thereof. Nevertheless, the diastereomeric excess of the oxetane product was greatly improved by about 40 %. This enhancement, which is not accompanied by any significant changes in the photophysical properties, is difficult to rationalize by conventional enthalpic control concepts based on repulsive steric and/or attractive intermolecular interactions as well as electronic perturbations. Differential activation parameters and compensatory enthalpy–entropy relationships revealed that the diastereoselectivity enhancement is not simply enthalpic but also entropic in origin.