Asymmetric Total Synthesis of (−)-Pavidolide B via a Thiyl-Radical-Mediated [3 + 2] Annulation Reaction

Zhang, Pengpeng; Li, Yuanhe; Yan, Zhiming; Gong, Jianxian; Yang, Zhen

doi:10.1021/acs.joc.9b02230

Cited by 15 publications

(15 citation statements)

References 82 publications

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“…These kaurane-type diterpenes A – C were therefore considered suitable precursors to initiate the synthesis of target compounds. Thus, compound 135 was obtained from the commercially available ( R )-(−)-carvone ( D ) ( Figure 3 ), which was first transformed into 5β-hydroxy-( R )-carvone ( E ) by chemoselective monohydroxylation and subsequently reduced to 2-oxo-menth-6-en-5β-ol ( F ) by selective hydrogenation using the Wilkinson’s catalyst [ 44 ].…”

Section: Resultsmentioning

confidence: 99%

“…Compound G was synthesized as previously reported [ 44 ]. Briefly, Cu–Al Ox catalyst (168 mg) was placed into a 100-mL round-bottom flask (RBF) containing absolute EtOH (30 mL).…”

Section: Methodsmentioning

confidence: 99%

“…Compound F was prepared as previously reported [ 44 ]. Briefly, RhCl (PPh 3 ) 3 (46.2 mg, 0.05 mmol, 5 mol%) was added to a 25-mL RBF containing a stirred solution of E (166 mg, 1.0 mmol, 1.0 equiv.)…”

Section: Methodsmentioning

confidence: 99%

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Identification of Kaurane-Type Diterpenes as Inhibitors of Leishmania Pteridine Reductase I

et al. 2021

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The current treatments against Leishmania parasites present high toxicity and multiple side effects, which makes the control and elimination of leishmaniasis challenging. Natural products constitute an interesting and diverse chemical space for the identification of new antileishmanial drugs. To identify new drug options, an in-house database of 360 kauranes (tetracyclic diterpenes) was generated, and a combined ligand- and structure-based virtual screening (VS) approach was performed to select potential inhibitors of Leishmania major (Lm) pteridine reductase I (PTR1). The best-ranked kauranes were employed to verify the validity of the VS approach through LmPTR1 enzyme inhibition assay. The half-maximal inhibitory concentration (IC50) values of selected bioactive compounds were examined using the random forest (RF) model (i.e., 2β-hydroxy-menth-6-en-5β-yl ent-kaurenoate (135) and 3α-cinnamoyloxy-ent-kaur-16-en-19-oic acid (302)) were below 10 μM. A compound similar to 302, 3α-p-coumaroyloxy-ent-kaur-16-en-19-oic acid (302a), was also synthesized and showed the highest activity against LmPTR1. Finally, molecular docking calculations and molecular dynamics simulations were performed for the VS-selected, most-active kauranes within the active sites of PTR1 hybrid models, generated from three Leishmania species that are known to cause cutaneous leishmaniasis in the new world (i.e., L. braziliensis, L. panamensis, and L. amazonensis) to explore the targeting potential of these kauranes to other species-dependent variants of this enzyme.

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Section: Resultsmentioning

confidence: 99%

“…Compound G was synthesized as previously reported [ 44 ]. Briefly, Cu–Al Ox catalyst (168 mg) was placed into a 100-mL round-bottom flask (RBF) containing absolute EtOH (30 mL).…”

Section: Methodsmentioning

confidence: 99%

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Identification of Kaurane-Type Diterpenes as Inhibitors of Leishmania Pteridine Reductase I

et al. 2021

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“…(A) The preparation of meloscine (158) features a cascade radical annulation of divinylcyclopropane [70]. (B) Thiyl-radical-mediated [3 + 2] annulation reaction realizes the synthesis of (−)-pavidolide B (166) [71,72]. (C) A Danheiser's [3 + 2] annulation en route to conidiogenone B (171) [73] (inset, the suggested mechanism based on Danheiser's proposal disclosed in 1981 [74].)…”

Section: All-carbon [3 + 2] Annulation In Natural Product Synthesismentioning

confidence: 99%

“…In 2017, Yang and co-workers disclosed the synthesis of (−)-pavidolide B (166) by using a thiyl-radical-mediated [3 + 2] annulation reaction to create four contiguous stereocenters on tricycle 162 in one step [71,72] (Scheme 13B). Exposure of ester 159 to PhSH [75], p-toluidine and a catalytic amount of Ir(dF(CF 3 )ppy) 2 (dtbbpy)PF 6 under the irradiation of blue LED light [76,77] afforded tricycle 162 in 50% yield.…”

Section: All-carbon [3 + 2] Annulation In Natural Product Synthesismentioning

confidence: 99%

All-carbon [3 + 2] cycloaddition in natural product synthesis

Wang¹,

Liu²

2020

Beilstein J. Org. Chem.

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Many natural products possess interesting medicinal properties that arise from their intriguing chemical structures. The highly-substituted carbocycle is one of the most common structural features in many structurally complicated natural products. However, the construction of highly-substituted, stereo-congested, five-membered carbocycles containing all-carbon quaternary center(s) is, at present, a distinct challenge in modern synthetic chemistry, which can be accessed through the all-carbon [3 + 2] cycloaddition. More importantly, the all-carbon [3 + 2] cycloaddition can forge vicinal all-carbon quaternary centers in a single step and has been demonstrated in the synthesis of complex natural products. In this review, we present the development of all-carbon [3 + 2] cycloadditions and illustrate their application in natural product synthesis reported in the last decade covering 2011–2020 (inclusive).

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Metathesis Reactions in Natural Product Fragments and Total Syntheses

et al. 2022

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The passion of total‐ and fragments syntheses of natural products always remained one of the top priorities among the synthetic chemists worldwide. Due their curiosity toward the complexity of molecules of living nature and their endeavour to imitate them in laboratory; limitless arrays of natural products have been extracted, architecturally‐elucidated, synthesized, and chronicled by utilizing various synthetic methodologies in different fashions. Frequently, the synthesis of complex natural products proceed with inscrutable synthetic challenges, which can be circumvented either by modification of previously developed synthetic methods or by formulating a new one. In this way, a myriad of powerful synthetic reactions have been developed since the genesis of the logic of chemical synthesis. Amongst them, metathesis tactics discovered unexpectedly in the 1950s (Nobel Prize in 2005), have incredibly influenced and changed the landscape of the art of the total and formal synthesis in the last three A. H. Hoveyda, A. R. Zhugralin, me abruptly as compared to other developed transformations or their modified forms. In this particular review article, we envisioned to report a comprehensive detail of the metathetic tools involved in both total and fragments synthesis of natural products in the years 2018 and 2019 along with an overview of 2017.

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Asymmetric Total Synthesis of (−)-Pavidolide B via a Thiyl-Radical-Mediated [3 + 2] Annulation Reaction

Cited by 15 publications

References 82 publications

Identification of Kaurane-Type Diterpenes as Inhibitors of Leishmania Pteridine Reductase I

Identification of Kaurane-Type Diterpenes as Inhibitors of Leishmania Pteridine Reductase I

All-carbon [3 + 2] cycloaddition in natural product synthesis

Metathesis Reactions in Natural Product Fragments and Total Syntheses

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