Synthesis of Demissidine by a Ring Fragmentation 1,3-Dipolar Cycloaddition Approach

Zhang, Zhe; Giampa, Geoffrey M.; Draghici, Cristian; Huang, Qiufeng; Brewer, Matthias

doi:10.1021/ol4004993

Cited by 22 publications

(23 citation statements)

References 18 publications

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“…For instance, Brewer and co-workers recently reported an efficient synthesis of steroidal alkaloid demissidine 31 from epiandrosterone 28 (Scheme 4a). 16 The key reaction in this synthetic route was a ring fragmentation reaction 17 of a γ-silyloxy-β-hydroxy-α-diazoester 29 in the presence of a Lewis acid to provide aldehyde tethered ynoate 30 in 75% yield. From intermediate 30, demissidine was obtained in six additional steps with the indolizidine framework installed via an azomethine ylide 1,3-dipolar cycloaddition.…”

Section: Synpacts Syn Lett 3 Reaction Developmentmentioning

confidence: 99%

Alkyne-Forming Furan Fragmentation: A General Method to Convert Furans into Alkynoic Acids

Deng

Gui

2019

Synlett

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Furans are readily available and highly reactive heterocycles that serve as versatile four-carbon synthons in organic synthesis. Recently, we discovered that furans, upon oxidation with singlet oxygen, can be transformed into alkynes via dual C–C double-bond cleavage. This Synpacts article presents an overview of the historical context and the development of this furan fragmentation reaction. We also discuss its application in natural product synthesis and a plausible reaction mechanism.1 Introduction2 Background of Alkyne-Forming Furan Fragmentation3 Reaction Development4 Conclusion

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Section: Synpacts Syn Lett 3 Reaction Developmentmentioning

confidence: 99%

Alkyne-Forming Furan Fragmentation: A General Method to Convert Furans into Alkynoic Acids

Deng

Gui

2019

Synlett

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“…So far, eight syntheses of solanidine and demissidine have been described, four of them in the last decade, and the latest one was reported last year [ 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 ]. Although recently invented methods brought a significant improvement, the described methods suffer from several drawbacks, such as multi-step procedures or unsatisfactory yields.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Demissidine Analogues from Tigogenin via Imine Intermediates

Wojtkielewicz

Kiełczewska

Baj

et al. 2021

IJMS

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A five-step transformation of a spiroketal side chain of tigogenin into an indolizidine system present in solanidane alkaloids such as demissidine and solanidine was elaborated. The key intermediate in the synthesis was spiroimine 3 readily obtained from tigogenin by its RuO4 oxidation to 5,6-dihydrokryptogenin followed by amination with aluminum amide generated in situ from DIBAlH and ammonium chloride. The mild reduction of spiroimine to a 26-hydroxy-dihydropyrrole derivative and subsequent mesylation resulted in the formation of 25-epidemissidinium salt or 23-sulfone depending on reaction conditions.

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“…An important application of chemical modification of steroid molecules is to synthesize compounds containing an additional fused ring. Steroids bearing an additional fused ring are common skeletons involved in many natural products [20][21][22][23][24] and pharmaceuticals [25][26][27]. It should be noted that some of these compounds exhibit no significant hormonal activity [28][29][30][31].…”

Section: Introductionmentioning

confidence: 99%

Novel d-Annulated Pentacyclic Steroids: Regioselective Synthesis and Biological Evaluation in Breast Cancer Cells

Vorontsova

Yadykov

Scherbakov³

et al. 2020

Molecules

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The acid-catalyzed cyclization of benzylidenes based on 16-dehydropregnenolone acetate (16-DPA) was studied. It was found that these compounds readily undergo regioselective interrupted Nazarov cyclization with trapping chloride ion and an efficient method of the synthesis of d-annulated pentacyclic steroids based on this reaction was proposed. The structures of the synthesized pentacyclic steroids were determined by NMR and X-ray diffraction. It was found that the reaction affords a single diastereomer, but the latter can crystallize as two conformers depending on the structure. Antiproliferative activity of synthesized compounds was evaluated against two breast cancer cell lines: MCF-7 and MDA-MB-231. All tested compounds showed relatively high antiproliferative activity. The synthetic potential of the protocol developed was illustrated by the gram-scale experiment.

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Synthesis of Demissidine by a Ring Fragmentation 1,3-Dipolar Cycloaddition Approach

Cited by 22 publications

References 18 publications

Alkyne-Forming Furan Fragmentation: A General Method to Convert Furans into Alkynoic Acids

Alkyne-Forming Furan Fragmentation: A General Method to Convert Furans into Alkynoic Acids

Synthesis of Demissidine Analogues from Tigogenin via Imine Intermediates

Novel d-Annulated Pentacyclic Steroids: Regioselective Synthesis and Biological Evaluation in Breast Cancer Cells

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