Copper-based bioinspired oxygenation and glyoxalase-like reactivity

Area of Science:

• Bioinorganic Chemistry
• Catalysis
• Biomimetic Chemistry

Background:

• Metalloenzyme models are crucial for developing biomimetic and bioinspired catalytic systems.
• Oxygenation of external substrates is a key challenge in catalysis.
• Understanding enzyme mechanisms aids in designing synthetic catalysts.

Purpose of the Study:

• To develop a novel biomimetic catalyst for substrate oxygenation.
• To achieve efficient conversion of acetone to lactate under mild conditions.
• To elucidate the reaction mechanism of this unprecedented transformation.

Main Methods:

• Reaction of a copper(I) complex, [(Cu(I)TpCF3,CH3)2], with excess acetone in the presence of air.
• Characterization of the product, [CuTpCF3,CH3)(lactate)], using structural analysis.
• Oxygenation studies with isotopically labeled acetone and water to probe the reaction pathway.

Main Results:

• The copper complex efficiently converted acetone to lactate in over 95% yield.
• The reaction proceeded in one pot at ambient conditions without ligand decomposition.
• An inner-sphere oxidation/isomerization mechanism was proposed based on product structure and isotopic labeling.

Conclusions:

• Structurally abbreviated metalloenzyme models can achieve complex bioinspired reactivity.
• This work demonstrates a novel and efficient biomimetic route for acetone to lactate conversion.
• The proposed mechanism provides insights into bioinspired catalysis and oxygenation reactions.