Photochemical Homologated Aminophosphorylation of Carbon‐Carbon π‐, and σ‐Bonds through Radical Translocation

Difunctionalization of olefins serves as the workhorse for rapid creation of molecular complexity from simple feedstocks. However, these reactions are mostly restricted to the 1,2‐variant, with higher homologations being attempted to a much lesser extent. Radical translocation strategies serve as an escape from the traditional 1,2‐strategies, providing a means for achieving distant functionalizations that are otherwise difficult to access. Herein, we disclose visible light‐mediated strategies for the accessing of 1,3‐, 1,4‐, 1,5‐, and 1,6‐aminophosphonates via combination of various radical shifting methods. In addition, the aminophosphorylation of σ ‐bonds was also achieved, leading to 1,3‐aminophosphorylated cyclobutanes.