Structure–Reactivity Correlations and Mechanistic Understanding of the Photorearrangement and Photosalient Effect of α-Santonin and Its Derivatives in Solutions, Crystals, and Nanocrystalline Suspensions

Abstract

The synthesis, crystal packing and photochemical reactions of α-santonin ( 1a ) and its methyl, ethyl, n -propyl, and n -butyl derivatives ( 1b – e ) are described to explore the effect that a photochemically benign yet structurally significant synthetic modification can have on the solid-state photochemical reactivity. The structures of the derivatives were determined using single crystal X-ray diffraction and compared against the packing of α-santonin. A cage dimer ( 12a ) found exclusively upon irradiation of 1a in the solid state was not found when the other derivatives were exposed to light, because the alkylation proved to perturb the crystal packing away from an optimal dimerization alignment. Using a high-speed camera, we monitored the photosalient effect of α-santonin and found it to occur at an angle orthogonal to the b -axis of the unit cell, which we suspect is caused by the formation of the cage dimer 12 . The photochemistry of 1a – e in solution and crystalline suspensions was also analyzed. The solution photochemistry was in accord with literature precedence, and the crystalline suspensions yielded a variety of photoproducts including a tertiary alcohol ( 7b – e ), which is not commonly observed in neutral water. An exocyclic alkene photoproduct ( 8b ) was also discovered, and its presence is hypothesized to be caused by an intermolecular deprotonation caused by a water molecule present in the crystal.