An Integrated Cofactor/Co‐Product Recycling Cascade for the Biosynthesis of Nylon Monomers from Cycloalkylamines

Abstract

We report a highly atom‐efficient integrated cofactor/co‐product recycling cascade employing cycloalkylamines as multifaceted starting materials for the synthesis of nylon building blocks. Reactions using E. coli whole cells as well as purified enzymes produced excellent conversions ranging from >80 and 95 % into desired ω‐amino acids, respectively with varying substrate concentrations. The applicability of this tandem biocatalytic cascade was demonstrated to produce the corresponding lactams by employing engineered biocatalysts. For instance, ϵ‐caprolactam, a valuable polymer building block was synthesized with 75 % conversion from 10 mM cyclohexylamine by employing whole‐cell biocatalysts. This cascade could be an alternative for bio‐based production of ω‐amino acids and corresponding lactam compounds.

Biocatalytic Cascade Synthesis of Enantioenriched Epoxides and Triols from Biomass‐Derived Synthons Driven by Specifically Designed Enzymes

“…Hence, in the past decade, the interest in tailored enzymatic cascades for the production of synthetic building blocks and more complex molecules, both in vitro and in vivo, has dramatically increased. [3][4][5][6][7][8][9][10] The enzyme 4-oxalocrotonate tautomerase (4-OT) is a versatile and powerful catalyst. In the past years, 4-OT was explored and evolved for catalyzing several chemically distinct transformations, mainly involving CÀ C bond formations.…”

“…Therefore, unwanted side reactions are usually avoided, and the desired molecule is typically obtained in high enantiopurity. Hence, in the past decade, the interest in tailored enzymatic cascades for the production of synthetic building blocks and more complex molecules, both in vitro and in vivo, has dramatically increased [3–10] …”

Concept of an Enzymatic Reactive Extraction Centrifuge

“…Additionally, multi-enzyme cascades provide further advantages for potential industrial application [3]. These are, for example, flexible reaction routes and no required separation of the intermediates or side products [4,5]. However, a big challenge remains economic competitiveness with well-established chemical processes [6].…”

Promoter engineering‐mediated Tuning of esterase and transaminase expression for the chemoenzymatic synthesis of sitagliptin phosphate at the kilogram‐scale

“…chemical products (Sarak et al, 2021;Wu et al, 2021). Such cascades allow us to operate more complex reaction systems in one-pot, resulting in higher yields.…”

“…esterase/lipase, promoter engineering, sitagliptin, transaminase Over the decades, there has been a surge in interest in multienzyme cascade reactions interest owing to their potential for producing a variety of pharmaceutical, agrochemical, and industrially important chemical products (Sarak et al, 2021;Wu et al, 2021). Such cascades allow us to operate more complex reaction systems in one-pot, resulting in higher yields.…”