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Photodecarboxylase from Chlorella variabillis ( Cv FAP) is one of the three known light‐activated enzymes that catalyzes the decarboxylation of fatty acids into the corresponding C1‐shortened alkanes. Although the substrate scope of Cv FAP has been altered by protein engineering and decoy molecules, it is still limited to mono‐fatty acids. Our studies demonstrate for the first time that long chain dicarboxylic acids can be converted by Cv FAP. Notably, the conversion of dicarboxylic acids to alkanes still represents a chemically very challenging reaction. Herein, the light‐driven enzymatic decarboxylation of dicarboxylic acids to the corresponding (C2‐shortened) alkanes using Cv FAP is described. A series of dicarboxylic acids is decarboxylated into alkanes in good yields by means of this approach, even for the preparative scales. Reaction pathway studies show that mono‐fatty acids are formed as the intermediate products before the final release of C2‐shortened alkanes. In addition, the thermostability, storage stability, and recyclability of Cv FAP for decarboxylation of dicarboxylic acids are well evaluated. These results represent an advancement over the current state‐of‐the‐art.

Fatty epoxides are unique building blocks in organic transformations and materials production; however, their synthetic methodologies are currently not accessible from renewable fatty acids. Herein, a photoenzymatic decarboxylation of epoxy fatty acids into fatty epoxides was demonstrated using fatty acid photodecarboxylase (FAP) from Chlorella variabilis NC64A (CvFAP). Various fatty epoxides were synthesized in excellent selectivity by wild‐type CvFAP. The decarboxylation reaction was also achieved with four new FAP homologues, potentially suggesting a broad availability of the biocatalysts for this challenging decarboxylation reaction. By combining CvFAP with lipase and peroxygenase, a multienzymatic cascade to transform oleic acid and its triglyceride into the corresponding fatty epoxides was established. The obtained fatty epoxides were further converted into rather unusual fatty compounds including diol, alcohol, ether, and chain‐shortened carboxylic acids. The present photobiocatalytic synthesis of fatty epoxides from natural starting materials excels by its intrinsic selectivity, mild conditions, and independence of nicotinamide cofactors.

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