An easy route toward enantio-enriched polycyclic derivatives via an asymmetric domino conjugate reduction–aldol cyclization catalyzed by a chiral Cu(I) complex

Deschamp, Julia; Hermant, Thomas; Riant, Olivier

doi:10.1016/j.tet.2011.07.039

Cited by 47 publications

(22 citation statements)

References 83 publications

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“…The naturally occurring pairwise activity of functionally distinct diTPSs in modular diterpene biosynthetic systems, inspires opportunities for metabolic engineering and synthetic biology platforms through combinatorial expression of diTPSs and possibly P450 enzymes selected from the large suite of cloned enzymes for the production of known natural, novel and non‐natural diterpene bioproducts (Ajikumar et al ., ; Dai et al ., ; Schalk et al ., ; Brückner and Tissier, ; Guo et al ., ). Although not at production scale, the formation of 9,13‐epoxy‐labd‐14‐ene by co‐expression of Mv CPS1 and Mv ELS in microbial and plant systems shown here, illustrates the possibility to produce marrubiin and other pharmaceutically active diterpenes in engineered biological systems as an alternative to multi‐step total syntheses (Mangoni et al ., ; Deschamp et al ., ).…”

Section: Discussionmentioning

confidence: 97%

Diterpene synthases of the biosynthetic system of medicinally active diterpenoids in Marrubium vulgare

et al. 2014

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SUMMARYMarrubium vulgare (Lamiaceae) is a medicinal plant whose major bioactive compounds, marrubiin and other labdane-related furanoid diterpenoids, have potential applications as anti-diabetics, analgesics or vasorelaxants. Metabolite and transcriptome profiling of M. vulgare leaves identified five different candidate diterpene synthases (diTPSs) of the TPS-c and TPS-e/f clades. We describe the in vitro and in vivo functional characterization of the M. vulgare diTPS family. In addition to MvEKS ent-kaurene synthase of general metabolism, we identified three diTPSs of specialized metabolism: MvCPS3 (+)-copalyl diphosphate synthase, and the functional diTPS pair MvCPS1 and MvELS. In a sequential reaction, MvCPS1 and MvELS produce a unique oxygenated diterpene scaffold 9,13-epoxy-labd-14-ene en route to marrubiin and an array of related compounds. In contrast with previously known diTPSs that introduce a hydroxyl group at carbon C-8 of the labdane backbone, the MvCPS1-catalyzed reaction proceeds via oxygenation of an intermediate carbocation at C-9, yielding the bicyclic peregrinol diphosphate. MvELS belongs to a subgroup of the diTPS TPS-e/f clade with unusual ba-domain architecture. MvELS is active in vitro and in vivo with three different prenyl diphosphate substrates forming the marrubiin precursor 9,13-epoxy-labd-14-ene, as identified by nuclear magnetic resonance (NMR) analysis, manoyl oxide and miltiradiene. MvELS fills a central position in the biosynthetic system that forms the foundation for the diverse repertoire of Marrubium diterpenoids. Co-expression of MvCPS1 and MvELS in engineered E. coli and Nicotiana benthamiana offers opportunities for producing precursors for an array of biologically active diterpenoids.

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Section: Discussionmentioning

confidence: 97%

Diterpene synthases of the biosynthetic system of medicinally active diterpenoids in Marrubium vulgare

et al. 2014

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“…[36] Some other examples of synthesized [m.n.p]fenestranes are: [3.5.3]fenestrane 7, [3.5.4]fenestranes 8, [37] and [4.4.4]fenestranes 9. [38] Figure 14). [39] Penifulvine A has interesting antifungal and insecticidal activities.…”

Section: Methodsmentioning

confidence: 99%

“…Chemie with the adduct 30·BF 3 (X-ray: 120. 38,121.38;DFT: 118.28,123.28). More recently, the nitroso-acetal 31 could also be obtained from vinylic ether 25 and nitroalkene 28 (Scheme 3).…”

Section: Methodsmentioning

confidence: 99%

Fenestranes in Synthesis: Unique and Highly Inspiring Scaffolds

et al. 2013

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The scaffold of fenestranes is quite unique, as it contains four condensed cycles and a distorted tetracoordinated central carbon atom with bond angles greater than the regular 109°28". In this Minireview, a detailed overview on the developments regarding this compound class, including their synthesis, is given for the time period since 2006. In the past years, natural products that belong to the class of heterofenestranes have been isolated and their syntheses will also be discussed.

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“…This was based on an enantioselective copper-catalyzed domino reductive Michael/aldol cyclization reaction. 49 As shown in Scheme 14, this domino process began with the reductive Michael reaction of a diketoester with phenylsilane performed in the presence of a chiral copper catalyst derived from a Taniaphos ligand, leading to…”

Section: Scheme 12mentioning

confidence: 99%

Syntheses of Natural and Biologically Relevant Products through Asymmetric Metal-Catalyzed Domino Reactions. A Review

Pellissier

2019

Organic Preparations and Procedures International

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An easy route toward enantio-enriched polycyclic derivatives via an asymmetric domino conjugate reduction–aldol cyclization catalyzed by a chiral Cu(I) complex

Cited by 47 publications

References 83 publications

Diterpene synthases of the biosynthetic system of medicinally active diterpenoids in Marrubium vulgare

Diterpene synthases of the biosynthetic system of medicinally active diterpenoids in Marrubium vulgare

Fenestranes in Synthesis: Unique and Highly Inspiring Scaffolds

Syntheses of Natural and Biologically Relevant Products through Asymmetric Metal-Catalyzed Domino Reactions. A Review

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