Concise Synthesis of (±)‐Aurantioclavine through a Base‐Promoted Pictet–Spengler Reaction

Yamada, Koji; Namerikawa, Yuichi; Haruyama, Tomohiro; Miwa, Yoshihisa; Yanada, Reiko; Ishikura, Minoru

doi:10.1002/ejoc.200900742

Cited by 52 publications

(20 citation statements)

References 17 publications

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“…only three steps from N b -benzyl-serotonine and alkylaldehydes by using this strategy. 7 Recently, we reported the first synthesis of the azepinoindole alkaloid hyrtioreticulins C and D through a base-promoted C-4 Pictet-Spengler reaction between tryptophan and acetaldehyde. 8 Although these results demonstrated that such a biomimetic cascade toward hyrtiazepines was possible, there were a few challenges in the synthesis of these alkaloids.…”

Section: Special Topic Syn Thesismentioning

confidence: 99%

C4 Pictet–Spengler Reactions for the Synthesis of Core Structures in Hyrtiazepine Alkaloids

2017

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The hyrtiazepine alkaloids are a family of bisindole natural products that have the azepinoindole backbone. We developed a biomimetic approach by constructing the azepinoindole core in a one-pot manner through 1,4-diazabicyclo[2.2.2]octane/2,2,2-trifluoroethanol (DABCO/TFE) promoted Pictet–Spengler reaction onto the C-4 position of tryptophan. This strategy allowed the synthesis of common key structures of these families. The key intermediate can be converted into the 3H-pyrano[2,3-b:5,6-e′]diindol intermediate present in hyrtimomines A and B, as well as the azepinoindole core present in fargesine.

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Section: Special Topic Syn Thesismentioning

confidence: 99%

C4 Pictet–Spengler Reactions for the Synthesis of Core Structures in Hyrtiazepine Alkaloids

2017

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“…27 Completed in just 3 linear steps and 21% overall yield from readily accessible starting materials, it represents the shortest total synthesis to date. The authors anticipated that the natural product could be obtained from the pivotal 5-hydroxy indole derivative 39 , which should be well-suited for further deoxygenation (Figure 5).…”

Section: Synthetic Approaches To Rearranged Clavine Alkaloids Covementioning

confidence: 99%

Total synthesis, biosynthesis and biological profiles of clavine alkaloids

McCabe

Wipf

2016

Org. Biomol. Chem.

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This review highlights noteworthy synthetic and biological aspects of the clavine subfamily of ergot alkaloids. Recent biosynthetic insights have laid the groundwork for a better understanding of the diverse biological pathways leading to these indole derivatives. Ergot alkaloids were among the first fungal-derived natural products identified, inspiring pharmaceutical applications in CNS disorders, migraine, infective diseases, and cancer. Pergolide, for example, is a semi-synthetic clavine alkaloid that has been used to treat Parkinson’s disease. Synthetic activities have been particularly valuable to facilitate access to rare members of the Clavine family and empower medicinal chemistry research. Improved molecular target identification tools and a better understanding of signaling pathways can now be deployed to further extend the biological and medical utility of Clavine alkaloids.

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“…Interestingly, the structures of Friedel-Crafts products 38–40 map closely onto the clavicipitic 28 and aurantioclavine 29 ergot alkaloids (Figure 2), where the unusual C–C bond between the indole and the isoprene unit is biosynthetically constructed through a Friedel-Crafts alkylation of tryptophan onto dimethylallyl diphosphate. 28,30 …”

Section: Cyclization Of Bisindoles 34 and 35mentioning

confidence: 99%

Electrophilic carbonyl activation: competing condensative cyclizations of tryptamine derivatives

Liu

Movassaghi

2015

Tetrahedron Letters

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A series of tryptamine derived bisindole substrates were subject to electrophilic activation of the functional grouping at their alpha-nitrogen in the form of iminium ions to enable cyclization onto the sterically hindered indole substructure. Our observations regarding divergent cyclization outcomes using electronically distinct bisindole substrates are described. Surprising preference for Friedel-Crafts alkylation reaction and evidence for an intriguing reversible spirocyclization are discussed.

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Concise Synthesis of (±)‐Aurantioclavine through a Base‐Promoted Pictet–Spengler Reaction

Abstract: A concise total synthesis of (±)‐aurantioclavine (1) was completed in three steps through the base‐promoted Pictet–Spengler reaction of Nb‐benzylserotonin with 3‐methylbut‐2‐enal. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Cited by 52 publications

References 17 publications

C4 Pictet–Spengler Reactions for the Synthesis of Core Structures in Hyrtiazepine Alkaloids

C4 Pictet–Spengler Reactions for the Synthesis of Core Structures in Hyrtiazepine Alkaloids

Total synthesis, biosynthesis and biological profiles of clavine alkaloids

Electrophilic carbonyl activation: competing condensative cyclizations of tryptamine derivatives

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