Natarajan, A.; Kaanumalle, L. E.; Jockusch, S.; Gibb, C.; Gibb, B. C.; Turro, N. J.; Ramamurthy, V. Controlling Photoreactions with Restricted Spaces and Weak Intermolecular Forces: Exquisite Product Selectivity during Oxidation of Olefins by Singlet Oxygen. Journal of the American Chemical Society 2007, 129, 4132-4133.
Publications by Year: 2007
Cavitand 1 is sufficiently predisposed to form nano-scale capsules in the presence of templating straight-chain hydrocarbons; quaternary complexes are formed when two copies of smaller guests are encapsulated, whilst larger guests form ternary entities.
The functionalization of deep-cavity cavitands via electrophilic substitution was investigated. In the parent structures, substitution occurs both at the exo position of the bowl-shaped hosts and on the convex face. Little or no endo substitution was observed. In contrast, derivatives in which methyl groups blocked the reaction sites on the convex face reacted selectively at the exo positions.
The water soluble capsule formed by a deep cavity cavitand with eight carboxylic acid groups controls product distribution during photo-Fries rearrangement of naphthyl esters in water by restricting the mobility of primary singletradical pair.