Decarboxylative Redox Bicyclo[1.1.1]pentylation: Benchmarking the Influence of Backbone Substituents on C–C Bond-Forming Reactions

The allylic substitution of α-(trifluoromethyl)styrenes was used to assess the feasibility of C-C bond formation to the bridgehead of bicyclo[1.1.1]pentanes via redox-active esters that fragment upon single-electron reduction. We observed that a 3-fluoro substituent on the backbone of the bicyclo[1.1.1]pentane induces behavior distinct from that with other electron-withdrawing groups as seen through diminished yields. The experimental results were supplemented with complementary computational studies to gain insights into the phenomena causing this dichotomy.