Cycloaddition-photochemical rearrangement stereocenter relay for the synthesis of x, y, z cage vectors

Here we present a fully diastereoselective synthesis of a trisubstituted nortricyclene scaffold via a cycloaddition–photochemical stereocenter relay strategy using a designed trifluoromethylated redoxactive ester dienophile. This synthetic approach enables precise stereo control over three distinct substituents positioned in orthogonal spatial directions. Unlike conventional three-dimensional benzene bioisosteres, which typically offer only two points of functionalization, our x, y, z-vector cage core provides a highly modular and transformable platform with three independent vectors in three-dimensional space. This designed unique trifluoromethylated building block opens new avenues for molecular diversification and functionalization, offering enhanced control over spatial orientation and reactivity.