Aromatic dioxygenases: molecular biocatalysis and applications

Area of Science:

• Biocatalysis and organic chemistry, focusing on enzymatic oxidation reactions.

Background:

• Aromatic dioxygenases are enzymes capable of catalyzing oxidation reactions.
• These enzymes can perform single and tandem oxidation reactions on conjugated polyenes.

Purpose of the Study:

• To explore the catalytic capabilities of aromatic dioxygenases in oxidizing conjugated polyenes.
• To investigate the rational selection and design of dioxygenases for controlling oxygenation regiochemistry and stereochemistry.
• To highlight the utility of resulting enantiopure bioproducts in chiral synthesis.

Main Methods:

• Rational selection and enzyme design of aromatic dioxygenases.
• Controlled oxygenation reactions using tailored dioxygenases and specific conjugated polyene substrates.
• Analysis of substrate features (shape, size, substitution) to influence reaction outcomes.

Main Results:

• Demonstrated the ability of aromatic dioxygenases to catalyze single and tandem oxidation of conjugated polyenes.
• Showcased successful control over regiochemistry and stereochemistry through enzyme engineering and substrate selection.
• Generated enantiopure bioproducts with high stereochemical purity.

Conclusions:

• Aromatic dioxygenases are versatile biocatalysts for the oxidation of conjugated polyenes.
• Enzyme engineering provides a powerful tool to precisely control the stereochemical and regiochemical outcomes of oxygenation.
• The enantiopure products derived from these enzymatic reactions serve as valuable precursors in developing novel chiral synthesis routes.