Manganese Terpyridine Artificial Metalloenzymes for Benzylic Oxygenation and Olefin Epoxidation
Tetrahedron 2014, 70, 4245-4249, 10.1016/j.tet.2014.03.008
New catalysts for non-directed hydrocarbon functionalization have great potential in organic synthesis. We hypothesized that incorporating a Mn-terpyridine cofactor into a protein scaffold would lead to artificial metalloenzymes (ArMs) in which the selectivity of the Mn cofactor could be controlled by the protein scaffold. We designed and synthesized a maleimide-substituted Mn-terpyridine cofactor and demonstrated that this cofactor could be incorporated into two different scaffold proteins to generate the desired ArMs. The structure and reactivity of one of these ArMs was explored, and the broad oxygenation capability of the Mn-terpyridine catalyst was maintained, providing a robust platform for optimization of ArMs for selective hydrocarbon functionalization.
Metal: MnLigand type: Poly-pyridineHost protein: Nitrobindin (Nb)Anchoring strategy: CovalentOptimization: ChemicalReaction: Peroxidation or oxygenationMax TON: 19.2ee: ---PDB: 3EMMNotes: ---
Metal: MnLigand type: Poly-pyridineHost protein: Nitrobindin (Nb)Anchoring strategy: CovalentOptimization: ChemicalReaction: EpoxidationMax TON: 19.8ee: ---PDB: 3EMMNotes: ---