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Caption : figure 1. most important retrosynthetic disconnections in the published ambruticin und jerangolid total syntheses.21–28

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Caption : figure 2. summary of the sar studies on the ambruticins and conclusions for the future generation of derivative libraries.

File Name : scheme 1.cdx

Caption : scheme 1. mendoza’s, martin’s and jacobsen’s total syntheses of ambruticin s (1a).21,22,24

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Caption : scheme 2. lee’s and hanessian’s total syntheses of ambruticin s (1a).23,25

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Caption : scheme 3. total syntheses of jerangolid d (2b), jerangolid a (2a), projerangolid (95) and jerangolid e (2d) as well as the non natural derivatives 5-epi-projerangolid (97) and 9-z-jerangolid e (97) (hahn et al.).26–28

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Caption : scheme 4. series of ambruticin derivatives obtained by semisynthesis.25,31–35

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Caption : scheme 5. synthetic, truncated ambruticin s derivatives of hanessian et al.25

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Caption : scheme 6. biosynthetic pathways to the jerangolids and ambruticins based on gene cluster analysis and gene knockout studies.18 blue: modules containing relevant tailoring domains. red: tailoring enzymes.

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Caption : scheme 7. in vitro studies on the key-enzymes for vinyl-thp formation.36–38

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Caption : scheme 8. proposed dvc formation in ambruticin biosynthesis (a) and studies on ambg (b).

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Caption : scheme 9. proposed chemoenzymatic syntheses of the jerangolids (a) and the ambruticins (b) that iteratively applies chemical synthetic sequences and cascades of biosynthesis enzymes. an optimised scenario is shown in which the backbone elongations between the enzymatic transformations are accomplished in one step.

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Caption : scheme 10. studies on the synthetic utility of the cyc ambdh3 and the o methyltransferase jerf.28,39,74