P450Jα: A New, Robust and α‐Selective Fatty Acid Hydroxylase Displaying Unexpected 1‐Alkene Formation

Abstract Oxyfunctionalization of fatty acids (FAs) is a key step in the design of novel synthetic pathways for biobased/biodegradable polymers, surfactants and fuels. Here, we show the isolation and characterization of a robust FA α‐hydroxylase (P450Jα) which catalyses the selective conversion of a broad range of FAs (C6:0‐C16:0) and oleic acid (C18:1) with H2O2 as oxidant. Under optimized reaction conditions P450Jα yields α‐hydroxy acids all with >95 % regioselectivity, high specific activity (up to 15.2 U mg−1) and efficient coupling of oxidant to product (up to 85 %). Lauric acid (C12:0) turned out to be an excellent substrate with respect to productivity (TON=394 min−1). On preparative scale, conversion of C12:0 reached 83 % (0.9 g L−1) when supplementing H2O2 in fed‐batch mode. Under similar conditions P450Jα allowed further the first biocatalytic α‐hydroxylation of oleic acid (88 % conversion on 100 mL scale) at high selectivity and in good yields (1.1 g L−1; 79 % isolated yield). Unexpectedly, P450Jα displayed also 1‐alkene formation from shorter chain FAs (≤C10:0) showing that oxidative decarboxylation is more widely distributed across this enzyme family than reported previously.