Accelerating a Mechanically Driven anti-Woodward–Hoffmann Ring Opening with a Polymer Lever Arm Effect

Mechanical forces have previously been used to drive reactions along pathways that violate the orbital symmetry effects captured in the Woodward-Hoffmann rules. Here, we show that a polymer "lever arm effect" can provide a mechanical advantage in accelerating the symmetry forbidden disrotatory ring opening of benzocyclobutene (BCB). Addition of an α-E-alkene to the BCB mechanophore drops the force required to induce reactions on the ∼0.1 s time scale of single-molecule force spectroscopy experiments from 1370 to 920 pN.