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Chemoenzymatic total synthesis of the antibiotic (−)-13-deoxytetrodecamycin using the Diels-Alderase TedJ

Title: Chemoenzymatic total synthesis of the antibiotic (−)-13-deoxytetrodecamycin using the Diels-Alderase TedJ
Authors: Russell SJ; Back CR; Perry C; Cheung KA; Maschio L; Charlton SN; Lees NR; Manzo-Ruiz M; Hayes MA; van der Kamp MW; Race PR; Willis CL
Source: Chemical Science, 17 September 2025
Publisher Information: Royal Society of Chemistry
Publication Year: 2025
Collection: Newcastle University Library ePrints Service
Description: © 2025 The Royal Society of Chemistry. The tetrodecamycins are tetracyclic natural products that exhibit potent antimicrobial activity against a multitude of drug-resistant pathogens. These compounds are structurally distinguished by the presence of a tetronate ring and trans-decalin with six contiguous asymmetric centres united by a seven-membered oxygen heterocycle. Herein we describe the first total synthesis of the antibiotic (−)-13-deoxytetrodecamycin. Our strategy is predicated on an enantioselective [4 + 2]-cycloaddition catalysed by the FAD-dependent Diels-Alderase TedJ, forming the trans-decalin with concomitant creation of two rings and four contiguous stereocenters with exquisite selectivity under mild conditions. In complementary studies, in vitro enzyme assays, X-ray crystallography and computational modelling are used to provide molecular insights into the TedJ catalysed reaction. These studies illustrate the power of adopting a chemoenzymatic approach for the enantioselective synthesis of a target compound which would be difficult to achieve using non-biological methods and provide a practical demonstration of the use of Diels-Alder biocatalysts in total synthesis. This approach has potentially widespread value in the global challenge of discovery and development of new antibiotics.
Document Type: article in journal/newspaper
File Description: application/pdf
Language: unknown
Relation: https://eprints.ncl.ac.uk/307913; https://eprints.ncl.ac.uk/fulltext.aspx?url=307913/92B03A6A-46FE-489B-9700-9E3E393823FD.pdf&pub_id=307913
Availability: https://eprints.ncl.ac.uk/307913
Rights: https://creativecommons.org/licenses/by/4.0/
Accession Number: edsbas.80325E0D
Database: BASE