Total synthesis of (+)-epiquinamide and (−)-epiepiquinamide from d-mannose

Sangsuwan, Withsakorn; Kongkathip, Boonsong; Chuawong, Pitak; Kongkathip, Ngampong

doi:10.1016/j.tet.2017.11.016

Cited by 12 publications

(6 citation statements)

References 23 publications

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“…Treatment of oxime 11b with cyanuric chloride in DMF at an elevated temperature afforded the arranged product as a 1:3 mixture of the cis (epiquinamide) to trans (epi-epiquinamide) amide 12 in a combined yield of 64%. The spectra data were identical to those reported …”

Section: Resultssupporting

confidence: 68%

“…To demonstrate the methodology, we develop a series of simple operations for synthesis of Dendrobatid alkaloid epi-epiquinamide (Scheme ). − Following the optimized oxidative cleavage conditions, trans quinolizidine 6b was transformed to trans -ketone 7b in 88% yield. Reduction with LiAlH 4 to reduce two carbonyl groups afforded a diastereomeric mixture of quinolizidine alcohol 9b in 74% yield.…”

Section: Resultsmentioning

confidence: 99%

“…The spectra data were identical to those reported. 32 In summary, we have reported a novel reaction, trisubstituted alkene-mediated domino hydroformylation/ double cyclization, to synthesize indolizidine, quinolizidine, and pyrrolidine-fused azepane skeleton from simple amide derivatives. Subsequent elaboration of the bicyclic product 6 into ketone 7 was effected by the optimized cleavage conditions and furnished a Dendrobatid alkaloid epi-epiquinamide in six steps.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Rh-Catalyzed Hydroformylation-Initiated Bicyclization: Construction of Azabicyclic Systems

2020

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Here, we describe the recent progress toward construction of 1-azabicyclic structures using a domino hydroformylation double cyclization strategy of an amide bearing the trisubstituted alkene functionality. The method provides a rapid and atom-economic access to alkaloid structures under mild conditions, especially for quinolizidine and pyrrolidine-fused azepane skeletons with yields up to 82% and good diastereoselectivity. Subsequent oxidative cleavage conditions are developed for the synthesis of Dendrobatid alkaloid epi-epiquinamide.

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Section: Resultssupporting

confidence: 68%

Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

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Rh-Catalyzed Hydroformylation-Initiated Bicyclization: Construction of Azabicyclic Systems

2020

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“…These molecules are organized under various transformations in the following sequence: 1) ring‐closing metathesis, 2) cross metathesis, 3) ring‐closing alkyne metathesis, and 4) ring‐closing enyne metathesis. 1) Ring‐closing metathesis : kanamienamide ( 37 ), [100] (+)‐chinensiolide B ( 38 ), [101] BMS‐846372 ( 39 ), [102] daphniyunnine B core ( 40 ), [103] clavilactone D ( 41 ), [104] pechueloic acid ( 42 ), [105] (−)‐deoxoapodine ( 43 ), [106] zephyranthine ( 44 ), [107] palodesangrens core ( 45 ), [108] (−)‐stemaphylline ( 46 ), [109] pavidolide B ( 47 ), [110] 7‐deoxypancratistatin ( 48 ), [111] (+)‐4‐ ɑ ‐dehydroxycrinamabine ( 49 ), [112] (−)‐elymoclavine ( 50 ), [113] viridin ( 51 ), [114] (−)‐crinane ( 52 ), [112] conduramine B‐1( 53 ), [115] ellipticine quinone ( 54 ), [116] (−)‐tegafur ( 55 ), [117] tetraponerine ( 56 ), [118] (−)‐cermizine B ( 57 ), [119] (Figure 7) (±)‐lycojaponicm ( 58 ), [120] (−)‐zeylenol ( 59 ), [121] aphanamal ( 60 ), [122] (+)‐epiquinamide ( 61 ), [123] erythrinane core ( 62 ), [124] (−)‐pseudodistomin E ( 63 ), [125] toxicodenane A ( 64 ), [126] ipomoeassin F ( 65 ), [127] scholarisine K ( 66 ), [128] panal core ( 67 ), [129] (+)‐crotanecine ( 68 ), [130] gagunin E analogue ( 69 ), [131] R‐(−)‐ ɑ ‐cuparenone ( 70 ), [132] citreamicin‐η core ( 71 ), [133] brianthein A core ( 72 ), [134] (+)‐cryptoconcatone H ( 73 ), [135] neomarchantin A ( 74 ), [136] (+)‐methynolide ( 75 ), [137] 10‐epi‐tirandamycin ( 76 ), [138] greensporone C ( 77 ), [139] 5′‐hydroxy‐zearalenone ( 78 ), [140] cheloviolene A ( 79 ), [141] crassifoside F c...…”

Section: Overview Of Natural Products Synthesized Via Metathesis Reac...mentioning

confidence: 99%

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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“…The sequence of reduction of lactam to enamine, its reprotonation to iminium ion under acidic conditions, and addition/cyclization of the generated nitronate ion gave a series of condensed biheterocycles of various sizes. One of these was exploited in the synthesis of (±)- epi -epiquinamide ( Figure 2G ) (Gregory et al, 2015 ), an alkaloid with as yet unidentified activity isolated from the skin extracts of an Ecuadorian poisonous frog Epipedobates tricolor (Sangsuwan et al, 2017 ).…”

Section: Natural Products Synthesismentioning

confidence: 99%

Reductive Functionalization of Amides in Synthesis and for Modification of Bioactive Compounds

Czerwiński

Furman

2021

Front. Chem.

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In this review, applications of the amide reductive functionalization methodology for the synthesis and modification of bioactive compounds are covered. A brief summary of the different protocols is presented in the introduction, followed by the synthetic application of these in late-stage functionalization, leading to known pharmaceuticals or to their derivatives, including bioisosteres, with potential higher activity as the main axis of the article. The synthetic approach to natural products based on amide reduction is also discussed; however, this is given in a condensed form focusing on recent or as yet unexplored applications due to a number of recently published excellent reviews covering this topic. The aim of this review is to illustrate the potential of reductive functionalization of amides as an elegant and useful tool in the synthesis of bioactive compounds and inspire further work in this field.

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Total synthesis of (+)-epiquinamide and (−)-epiepiquinamide from d-mannose

Cited by 12 publications

References 23 publications

Rh-Catalyzed Hydroformylation-Initiated Bicyclization: Construction of Azabicyclic Systems

Rh-Catalyzed Hydroformylation-Initiated Bicyclization: Construction of Azabicyclic Systems

Metathesis Reactions in Natural Product Fragments and Total Syntheses

Reductive Functionalization of Amides in Synthesis and for Modification of Bioactive Compounds

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