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. 2021 Mar 4;60(15):8081–8088. doi: 10.1002/anie.202014671

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© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.

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A) Scheme of the proposed sandarazol BGC and sandarazol biosynthesis by its megasynthase including the corresponding tailoring reactions. B) β‐branching reaction cascade to form the branched‐chain tail group. C) Reaction cascade that leads to the formation of two isomerized double bonds. D) Reaction sequence that supplies the amino acid l‐Dap to module 6 of the assembly line (arrows: genes; circles: domains; A: adenylation; ACP/PCP: acyl/peptidyl carrier protein; AT: acyl transferase; C: condensation; CMT/NMT: C/N methyl transferase; DH: dehydratase; E: epimerization; ECH: enoyl‐CoA hydratase; HAL: halogenase; HMG: hydroxymethylglutaryl‐CoA synthase; KR: ketoreductase; KS: ketosynthase; PLP: pyridoxal‐phosphate‐dependent enzyme; RED: reductase; TE: thioesterase; OX: oxidation).