Oxidative rearrangements during fungal biosynthesis

Cox, Russell J.

doi:10.1039/c4np00059e

Cited by 55 publications

(53 citation statements)

References 87 publications

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“…552 As noted in Section 2 the hallmark of iron-based oxygenases are the involvement of carbon-centered radicals at different stages in the catalytic cycles and those can drive scaffold rearrangements, both to larger and smaller rings systems.…”

Section: Oxidative Ring Rearrangementmentioning

confidence: 98%

Oxidative Cyclization in Natural Product Biosynthesis

et al. 2016

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Oxidative cyclizations are important transformations that occur widely during natural product biosynthesis. The transformations from acyclic precursors to cyclized products can afford morphed scaffolds, structural rigidity and biological activities. Some of the most dramatic structural alterations in natural product biosynthesis occur through oxidative cyclization. In this review, we examine the different strategies used by Nature to create new intra-(inter-)-molecular bonds via redox chemistry. The review will cover both oxidation- and reduction-enabled cyclization mechanisms, with an emphasis on the former. Radical cyclizations catalyzed by P450, nonheme iron, α-KG dependent oxygenases and radical SAM enzymes are discussed to illustrate the use of molecular oxygen and S-adenosylmethionine to forge new bonds at unactivated sites via one-electron manifolds. Nonradical cyclizations catalyzed by flavin-dependent monooxygenases and NAD(P)H-dependent reductases are covered to show the use of two-electron manifolds in initiating cyclization reactions. The oxidative installation of epoxides and halogens into acyclic scaffolds to drive subsequent cyclizations are separately discussed as examples of “disappearing” reactive handles. Lastly, oxidative rearrangement of rings systems, including contractions and expansions will be covered.

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Section: Oxidative Ring Rearrangementmentioning

confidence: 98%

Oxidative Cyclization in Natural Product Biosynthesis

et al. 2016

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“…Subsequently, an alternative mechanism has been proposed, since the above-described mechanism requires a chemically unfavorable syn-rearrangement. 98 The other scheme involves the cyclopropane intermediate 138, which is further rearranged to 139 with the spiro-lactone moiety. The enzymatic reaction is hereby completed by the rebound of the hydroxyl radical to 139 to yield 140, which undergoes spontaneous dehydration to produce 120 (Path B-1).…”

Section: Biosyntheses Of Austinol/dehydroaustinol and Related Compoundsmentioning

confidence: 99%

Biosynthesis of fungal meroterpenoids

2016

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Covering: up to September 2015. Meroterpenoids are hybrid natural products that partially originate from the terpenoid pathway. The meroterpenoids derived from fungi display quite diverse structures, with a wide range of biological properties. This review summarizes the molecular bases for their biosyntheses, which were recently elucidated with modern techniques, and also discusses the plausible biosynthetic pathways of other related natural products lacking genetic information. (Complementary to the coverage of literature by Geris and Simpson in Nat. Prod. Rep., 2009, 26, 1063-1094.).

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“…Aflatoxin biosynthesis has been studied since the late 1960s and has attracted attention, because the polyketide undergoes a series of oxidative rearrangements, which drastically alter the molecular scaffold. Due to the complexity of these processes, we will focus on the steps directly associated with heterocycle formation [ 82 – 84 ].…”

Section: Reviewmentioning

confidence: 99%

“… Overview on aflatoxin B1 ( 94 ) biosynthesis. HOMST = 11-hydroxy- O -methylsterigmatocystin [ 78 – 79 82 – 106 ]. …”

Section: Reviewmentioning

confidence: 99%

Biosynthesis of oxygen and nitrogen-containing heterocycles in polyketides

Hemmerling

Hahn

2016

Beilstein J. Org. Chem.

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SummaryThis review highlights the biosynthesis of heterocycles in polyketide natural products with a focus on oxygen and nitrogen-containing heterocycles with ring sizes between 3 and 6 atoms. Heterocycles are abundant structural elements of natural products from all classes and they often contribute significantly to their biological activity. Progress in recent years has led to a much better understanding of their biosynthesis. In this context, plenty of novel enzymology has been discovered, suggesting that these pathways are an attractive target for future studies.

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Oxidative rearrangements during fungal biosynthesis

Cited by 55 publications

References 87 publications

Oxidative Cyclization in Natural Product Biosynthesis

Oxidative Cyclization in Natural Product Biosynthesis

Biosynthesis of fungal meroterpenoids

Biosynthesis of oxygen and nitrogen-containing heterocycles in polyketides

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