Design Principles for Activating Organohalides with Hydrogen-Derived Electrons

Replacing wasteful metal-based reducing agents with H2 is an important goal for green chemistry. For this reason, we outline our design principles for building catalysts that use electrons from hydrogen to activate organohalides for reaction. These designs rely on an electron-withdrawing ligand to support low-valent metal centers, an electron-donating ligand to support oxidative addition, and the capacity for vacant sites to allow substrate docking. We begin by outlining our previous work in this field before describing a new rhodium complex that activates a particularly stubborn organohalide, 2,2-dibromopropane, using electrons from hydrogen. We then react this activated organohalide with styrene to generate a synthetically useful fragment of murraol in an efficient manner.