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Efficient Synthesis of Phenylacetate and 2‐Phenylethanol by Modular Cascade Biocatalysis

The green and sustainable synthesis of chemicals from renewable feedstocks by a biotransformation approach has gained increasing attention in recent years. In this work, we developed enzymatic cascades to efficiently convert l‐phenylalanine into 2‐phenylethanol (2‐PE) and phenylacetic acid (PAA), l‐tyrosine into tyrosol (p‐hydroxyphenylethanol, p‐HPE) and p‐hydroxyphenylacetic acid (p‐HPAA). The enzymatic cascade was cast into an aromatic aldehyde formation module, followed by an aldehyde reduction module, or aldehyde oxidation module, to achieve one‐pot biotransformation by using recombinant Escherichia coli. Biotransformation of 50 mM l‐Phe produced 6.76 g/L PAA with more than 99 % conversion and 5.95 g/L of 2‐PE with 97 % conversion. The bioconversion efficiencies of p‐HPAA and p‐HPE from l‐Tyr reached to 88 and 94 %, respectively. In addition, m‐fluoro‐phenylalanine was further employed as an unnatural aromatic amino acid substrate to obtain m‐fluoro‐phenylacetic acid; >96 % conversion was achieved. Our results thus demonstrated high‐yielding and potential industrial synthesis of above aromatic compounds by one‐pot cascade biocatalysis.