Transforming Inert Cycloalkanes into α,ω‐Diamines by Designed Enzymatic Cascade Catalysis

Abstract Aliphatic α,ω‐diamines (DAs) are important monomer precursors that are industrially produced by energy‐intensive, multistage chemical reactions that are harmful to the environment. Therefore, the development of sustainable green DA synthetic routes is highly desired. Herein, we report an efficient one‐pot in vivo biocatalytic cascade for the transformation of cycloalkanes into DAs with the aid of advanced techniques, including the RetroBioCat tool for biocatalytic route design, enzyme mining for finding appropriate enzymes and microbial consortia construction for efficient pathway assembly. As a result, DAs were successfully produced by the designed microbial consortia‐based biocatalytic system. In particular, the highest biosynthesis productivity record of 1,6‐hexanediamine was achieved when using either cyclohexanol or cyclohexane as a substrate. Thus, the developed biocatalytic process provides a promising alternative to the dominant industrial process for manufacturing DAs.