Unspecific peroxygenase enabled formation of azoxy compounds

Area of Science:

• Biocatalysis and Organic Synthesis
• Enzymology
• Chemical Reactions

Background:

• Enzymes are increasingly used in chemical synthesis, but their application scope is limited compared to traditional organic synthesis.
• Azoxy products are a class of compounds rarely synthesized using enzymatic catalysts.
• Expanding biocatalysis to new product classes like azoxy compounds is crucial for sustainable chemistry.

Purpose of the Study:

• To investigate fungal unspecific peroxygenases as catalysts for azoxy product synthesis.
• To explore the potential of biocatalysis in the underexplored area of azoxy compound formation.
• To demonstrate the efficiency and selectivity of peroxygenase-catalyzed azoxy synthesis.

Main Methods:

• Utilized fungal unspecific peroxygenases for the synthesis of azoxy products.
• Employed simple aniline derivatives as starting materials.
• Characterized catalytic performance, including turnover numbers, turnover frequency, conversion, and chemoselectivity.

Main Results:

• Discovered fungal unspecific peroxygenases as effective catalysts for azoxy product synthesis.
• Achieved high catalytic efficiency with up to 48,450 turnovers and a turnover frequency of 6.7 s^-1.
• Demonstrated excellent substrate transformation with up to 99% conversion and 98% chemoselectivity.

Conclusions:

• Fungal unspecific peroxygenases show significant promise for synthesizing azoxy products.
• The proposed mechanism involves spontaneous non-enzymatic formation of azoxy products from peroxygenase-derived intermediates.
• This study broadens the scope of biocatalytic transformations for azoxy compound synthesis.