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Synfacts 2025; 21(04): 403
DOI: 10.1055/a-2539-3577
Organo- and Biocatalysis

Photoredox- and Metalloenzyme-Catalysis Enables Enantioselective Radical Azidations and Thiocyanations

Contributor(s):
Benjamin List 
,
Lennart J. Brücher
Rui J, Mu X, Soler J, Paris JC, Guo Y *, Garcia-Borràs M *, Huang X *. Carnegie Mellon University, Pittsburgh, Johns Hopkins University, Baltimore, USA, and Universitat de Girona, Spain
Merging Photoredox with Metalloenzymatic Catalysis for Enantioselective Decarboxylative C(sp3 )–N3 and C(sp3 )–SCN Bond Formation.

Nat. Catal. 2024;
7: 1394-1403
DOI: 10.1038/s41929-024-01257-7
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Keywords

radical biocatalysis - photoredox - metalloenzymes - azidation - thiocyanation - N-hydroxyphthalimide esters

Significance

Huang and co-workers combined photoredox- and metalloenzyme-catalysis and developed an enantioselective decarboxylative azidation and thiocyanation of N-hydroxyphthalimide esters. Using eosin Y as photocatalyst and an engineered 4-hydroxyphenylpyruvate dioxygenase as enzyme, the desired products are obtained in low to good yields with low to high enantioselectivities.


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Comment

By combining photoredox chemistry for radical generation and enzyme catalysis for enantioselective radical capture, the authors gained control over challenging radical chemistry and expanded the scope of radical biocatalysis. Besides the proposed mechanism shown (PC* first oxidizes FeII), an alternative pathway starting with the reduction of the substrate could not be ruled out.


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Publication History

Article published online:
25 March 2025

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