Synthesis of (±)-γ-Rubromycin via a New Hypoiodite-Catalytic Oxidative Cycloetherification

Wei, Liping; Xue, Jiangeng; Liu, Hongbiao; Wang, Wenjing; Li, Ying

doi:10.1021/ol3024874

Cited by 35 publications

(18 citation statements)

References 41 publications

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“…Attempted synthesis of the mono(benzannulated) spiroacetals 379 using this method failed. [179][180][181] The same research group has recently applied this method to a formal synthesis of γ-rubromycin 58 [188] (Scheme 91). Treatment of phenol 380 with hypoiodite in the presence of TBAF as a fluoride ion source afforded the 5,6-bis(benzannulated) Scheme 89 IHA-based syntheses of cryptoacetalide and danshenspiroketallactone [183,184] Scheme 90 Xue et al's hypoiodite approach toward bis(benzannulated) spiroacetals [187] spiroacetal 381 in high yield.…”

Section: Furan Oxidation Strategies Toward Spiroacetalsmentioning

confidence: 99%

Synthesis of 5,6- and 6,6-Spirocyclic Compounds

Brimble

Stubbing

2013

Synthesis of Saturated Oxygenated Heterocycles I

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Section: Furan Oxidation Strategies Toward Spiroacetalsmentioning

confidence: 99%

Synthesis of 5,6- and 6,6-Spirocyclic Compounds

Brimble

Stubbing

2013

Synthesis of Saturated Oxygenated Heterocycles I

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“…Besides the diverse bioactivity, the complex intriguing spiroketal core of rubromycins has attracted the attention of several research groups for chemical synthesis and biosynthesis studies. Several total synthesis strategies have been successfully established for rubromycin compounds, whereas, the biosynthetic conversions of rubromycins still exist a lot uncertainties [11][12][13][14][15]. With the clear recognition of biosynthetic gene clusters of rubromycins, further studies of the individual enzymes are required to determine the exact biosynthetic pathway.…”

Section: Introductionmentioning

confidence: 99%

Characterization of Streptomyces piniterrae sp. nov. and Identification of the Putative Gene Cluster Encoding the Biosynthesis of Heliquinomycins

et al. 2020

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A novel actinomycete producing heliquinomycin and 9’-methoxy-heliquinomycin, designated strain jys28T, was isolated from rhizosphere soil of Pinus yunnanensis and characterized using a polyphasic approach. The strain had morphological characteristics and chemotaxonomic properties identical to those of members of the genus Streptomyces. It formed spiral chains of spores with spiny surfaces. The menaquinones detected were MK-9(H6), MK-9(H8) and MK-9(H4). The major fatty acids were iso-C16:0, C15:0, C16:1ω7с and anteiso-C15:0. The phospholipids were diphosphatidylglycerol, phosphatidylmethylethanolamine, phosphatidylethanolamine and phosphatidylinositol mannoside. The DNA G + C content of the draft genome sequence, consisting of 8.5 Mbp, was 70.6%. Analysis of the 16S rRNA gene sequence showed that strain jys28T belongs to the genus Streptomyces with the highest sequence similarities to Streptomyces chattanoogensis NBRC 13058T (99.2%) and Streptomyces lydicus DSM 40002T (99.2%) and phylogenetically clustered with them. Multilocus sequence analysis based on five other house-keeping genes (atpD, gyrB, rpoB, recA and trpB) and the low level of DNA–DNA relatedness and phenotypic differences allowed the novel isolate to be differentiated from its most closely related strains. Therefore, the strain is concluded to represent a novel species of the genus Streptomyces, for which the name Streptomyces piniterrae sp. nov. is proposed. Furthermore, the putative biosynthetic gene cluster of heliquinomycins was identified and the biosynthetic pathway was discussed. The type strain is jys28T (=CCTCC AA 2018051T =DSM 109823T).

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“…[14] Thus, the acidcatalyzed spiroketalization is almost completely inhibited in the case of isocoumarin-substituted substrates due to the decreased nucleophilicity of the phenolic oxygen atom. [4,15] The replacement of the isocoumarin fragment by a synthetic equivalent allowed Brimble (2009) [16] and Li (2012) [17] to achieve acid-induced spiroketalizations which led to formal total syntheses of (AE)-g-rubromycin. [18] We here report our route to this natural product, which afforded the target molecule in larger quantities by a convergent approach and highly efficient reaction steps.…”

mentioning

confidence: 99%

A Convergent Total Synthesis of the Telomerase Inhibitor (±)‐γ‐Rubromycin

Wilsdorf

Reißig

2014

Angew Chem Int Ed

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The total synthesis of the human telomerase inhibitor γ-rubromycin in its racemic form was accomplished in 3.8 % overall yield. The key feature of this synthesis is an efficient acid-catalyzed spiroketalization for the construction of the spiroketal core. The required electronically well-balanced spiroketal precursor was obtained by the convergent assembly of a naphthyl-substituted aldehyde, an α-methoxyallyl-γ-silyl-substituted phosphonate as the central C3 building block, and a highly functionalized aryl Grignard reagent. Another key feature is the late-stage construction of the isocoumarin moiety and a simultaneous protodesilylation furnishing the known methyl aryl ether protected precursor of γ-rubromycin.

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Synthesis of (±)-γ-Rubromycin via a New Hypoiodite-Catalytic Oxidative Cycloetherification

Cited by 35 publications

References 41 publications

Synthesis of 5,6- and 6,6-Spirocyclic Compounds

Synthesis of 5,6- and 6,6-Spirocyclic Compounds

Characterization of Streptomyces piniterrae sp. nov. and Identification of the Putative Gene Cluster Encoding the Biosynthesis of Heliquinomycins

A Convergent Total Synthesis of the Telomerase Inhibitor (±)‐γ‐Rubromycin

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