Selectivity control in electron spin inversion processes: regio- and stereochemistry of Paternò-Büchi photocycloadditions as a powerful tool for mapping intersystem crossing processes.

Regio- and stereoselectivity in ene-carbonyl photocycloadditions depend on the spin multiplicity of the excited carbonyl state, although both singlet and triplet states produce the cycloadducts with comparable chemoselectivity. The correlation between selectivity and spin state was evaluated by concentration, temperature, and solvent viscosity studies. The higher selectivity observed for triplet reactions is rationalized by the optimal conformations of the intermediate 2-oxabutane-1,4-diyls for intersystem crossing (ISC) to the singlet manifold, controlled preferentially by spin-orbit coupling. This weak interaction connected with ISC can lead to substantial control of regio- and stereoselectivity. The role of hyperfine coupling is demonstrated by magnetic isotope effects.