Calyciphylline B-Type Alkaloids: Total Syntheses of (−)-Daphlongamine H and (−)-Isodaphlongamine H

Hugelshofer, Cedric L.; Palani, Vignesh; Sarpong, Richmond

doi:10.1021/jacs.9b03576

Cited by 62 publications

(20 citation statements)

References 55 publications

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“…The intermolecular variant shows a wide alkyne scope, but in terms of the olefin counterpart is limited to the use of ethylene or strained alkenes, such as norbornene and norbornadiene. The high prevalence of five-membered ring systems in natural products, pharmaceuticals and other addedvalue compounds accounts for the great applicability that this reaction has found [26][27][28][29][30][31][32]. Despite the increasing demand of fluorinated compounds and the impressive development of the PKR, the combination of these two fields has been understudied, making it an exciting field of research.…”

Section: Review the Pauson-khand Reactionmentioning

confidence: 99%

Pauson–Khand reaction of fluorinated compounds

Escorihuela¹,

Sedgwick²,

Llobat³

et al. 2020

Beilstein J. Org. Chem.

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The Pauson–Khand reaction (PKR) is one of the key methods for the construction of cyclopentenone derivatives, which can in turn undergo diverse chemical transformations to yield more complex biologically active molecules. Despite the increasing availability of fluorinated building blocks and methodologies to incorporate fluorine in compounds with biological interest, there have been few significant advances focused on the fluoro-Pauson–Khand reaction, both in the inter- and intramolecular versions. Furthermore, the use of vinyl fluorides as olefinic counterparts had been completely overlooked. In this review, we collect the advances both on the stoichiometric and catalytic intermolecular and intramolecular fluoro-Pauson–Khand reaction, with special attention to the PKR of enynes containing a fluoride moiety.

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Section: Review the Pauson-khand Reactionmentioning

confidence: 99%

Pauson–Khand reaction of fluorinated compounds

Escorihuela¹,

Sedgwick²,

Llobat³

et al. 2020

Beilstein J. Org. Chem.

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show abstract

“…Hugelshofer, Sarpong, and co‐workers reported the first total synthesis of (−)‐daphlongamine H 502 (Scheme 74), a Daphniphyllum alkaloid with complex hexacyclic scaffold [255] . During their synthetic approach for the construction of this vital natural product, RCM was utilized to produce a cyclopentene derivative.…”

Section: Ring‐closing Metathesis (Rcm)mentioning

confidence: 99%

“…Hugelshofer, Sarpong, and co-workers reported the first total synthesis of (À )-daphlongamine H 502 (Scheme 74), a Daphniphyllum alkaloid with complex hexacyclic scaffold. [255] During their synthetic approach for the construction of this vital natural product, RCM was utilized to produce a cyclopentene derivative. Removal of sulfinyl group and clevage of the lactone ring from diene 498 with HCl followed by N-allylation with 2,3dibromoprop-1-ene delivered an amide derivative 499, which upon protection with TBS group and amidation with Ac 2 O provided the amide 500.…”

Section: Total Synthesis Of Natural Products Based On Rcmmentioning

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 latter, under hydrogenation conditions, underwent a rapid isomerization to the corresponding endocyclic enamide (not shown), which was diastereoselectively reduced. Further elaboration of the two remaining carbocyclic rings through a Pauson‐Khand process as well as the lactone ring furnished the aforementioned calyciphylline B‐type alkaloids …”

Section: From Halocompoundsmentioning

confidence: 99%

Radical Reactions in Alkaloid Synthesis: A Perspective from Carbon Radical Precursors

Bonjoch

Diaba

2020

Eur J Org Chem

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The usefulness of radical reactions in alkaloid synthesis is reviewed from the perspective of the functional groups embedded in the molecular structure of synthetic intermediates, that act as precursors of carbon‐centered radicals in the construction of new C–C bonds. The functional groups featured are alkenes, alkynes, halides (alkyl, vinyl, aryl), xanthates, sulfides, selenides, aldehydes, ketones, carboxylic acid derivatives (selenoesters, haloacetamides), β‐dicarbonyl compounds, and α‐heterosubstituted nitrogen‐compounds. The use of nitrogen‐centered radicals for C–N bond formation is also covered. Among the variety of radical processes applied, the most predominant are the hydride reductive method (Sn, Si), atom transfer radical reactions (Cu, Ru, B), and single‐electron transfer radical reactions promoted by Sm, Ni, Fe, Mn, Ti, and Ag. This review showcases the role radical reactions have played in the recent development of new strategies in alkaloid synthesis, as well as the implementation of new radical procedures in demanding substrates.

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Calyciphylline B-Type Alkaloids: Total Syntheses of (−)-Daphlongamine H and (−)-Isodaphlongamine H

Cited by 62 publications

References 55 publications

Pauson–Khand reaction of fluorinated compounds

Pauson–Khand reaction of fluorinated compounds

Metathesis Reactions in Natural Product Fragments and Total Syntheses

Radical Reactions in Alkaloid Synthesis: A Perspective from Carbon Radical Precursors

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