A pyrone remodeling strategy to access diverse heterocycles: application to the synthesis of fascaplysin natural products

Palani, Vignesh; Perea, Melecio A.; Gardner, Kristen E.; Sarpong, Richmond

doi:10.1039/d0sc06317g

Cited by 18 publications

(8 citation statements)

References 63 publications

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“…An iterative coupling sequence using 24 with pyrone derivatives ( 22 ) was then explored. Given our group’s interest in the utility of dibromopyrone 22a for natural product syntheses through site-selective cross-coupling reactions, we initially sought to take advantage of our insights into the reactivity of 22a in applying it to preparation of indanone-pyrone 25a . Unfortunately, in this case, when 22a was subjected to iterative coupling reaction conditions with 24 , we did not observe any productive reactions, presumably because the electron-deficient dibromopyrone 22a underwent rapid degradation under the basic reaction conditions.…”

Section: Resultsmentioning

confidence: 99%

Unified Total Syntheses of Benzenoid Cephalotane-Type Norditerpenoids: Cephanolides and Ceforalides

et al. 2022

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Detailed herein are our synthetic studies toward the preparation of the C18- and C19-benzenoid cephalotane-type norditerpenoids. Guided by chemical network analysis, the core structure of this natural product family was constructed in a concise manner using an iterative cross-coupling, followed by a formal inverse-electron-demand [4 + 2] cycloaddition. Initial efforts to functionalize an alkene group in the [4 + 2] cycloadduct using a Mukaiyama hydration and a subsequent olefination led to the complete C18-carbon framework. While effective, this approach proved lengthy and prompted the development of a direct alkene difunctionalization that relies on borocupration to advance the cycloadduct to the natural products. Late-stage peripheral C–H functionalization facilitated access to all of the known cephanolides in 6–10 steps as well as five recently isolated ceforalides in 8–13 steps.

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Section: Resultsmentioning

confidence: 99%

Unified Total Syntheses of Benzenoid Cephalotane-Type Norditerpenoids: Cephanolides and Ceforalides

et al. 2022

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“…We divided these derivatives into major categories according to the tested activity, and then subdivided derivatives according to the modified site. A cyclization strategy can also be used to synthesize fascaplysin (Scheme 4) [59,60]. Synthesis of 14 based on indole pyranone (13) and sodium methoxide.…”

Section: Structural Modificationmentioning

confidence: 99%

Marine-Derived Lead Fascaplysin: Pharmacological Activity, Total Synthesis, and Structural Modification

Wang

et al. 2023

Marine Drugs

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Fascaplysin is a planar structure pentacyclic alkaloid isolated from sponges, which can effectively induce the apoptosis of cancer cells. In addition, fascaplysin has diverse biological activities, such as antibacterial, anti-tumor, anti-plasmodium, etc. Unfortunately, the planar structure of fascaplysin can be inserted into DNA and such interaction also limits the further application of fascaplysin, necessitating its structural modification. In this review, the biological activity, total synthesis and structural modification of fascaplysin will be summarized, which will provide useful information for pharmaceutical researchers interested in the exploration of marine alkaloids and for the betterment of fascaplysin in particular.

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“…43,44 Recently, Sarpong and coworkers also studied a method to access pyrido[1,2-a]indole scaffolds starting from indole− pyrone adducts (Scheme 73). 319 For one of the substrates, they conducted a site-selective C3 coupling between indole boronate ester 263 and 3,4-dibromo-2-pyrone (59) under the previously disclosed C3 coupling conditions 92,94,308 to give the indole−pyrone adduct 264. Upon the ring-opening of 264 with sodium methoxide to reveal intermediate 264a, a spontaneous intramolecular cyclization proceeded to furnish pyrido[1,2-a]indole 264b in 29% yield.…”

Section: Solvent/additive Controlmentioning

confidence: 99%

Site-Selective Cross-Coupling of Polyhalogenated Arenes and Heteroarenes with Identical Halogen Groups

2021

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Methods to functionalize arenes and heteroarenes in a site-selective manner are highly sought after for rapidly constructing value-added molecules of medicinal, agrochemical, and materials interest. One effective approach is the site-selective cross-coupling of polyhalogenated arenes bearing multiple, but identical, halogen groups. Such cross-coupling reactions have proven to be incredibly effective for site-selective functionalization. However, they also present formidable challenges due to the inherent similarities in the reactivities of the halogen substituents. In this Review, we discuss strategies for site-selective cross-couplings of polyhalogenated arenes and heteroarenes bearing identical halogens, beginning first with an overview of the reaction types that are more traditional in nature, such as electronically, sterically, and directing-group-controlled processes. Following these examples is a description of emerging strategies, which includes ligand- and additive/solvent-controlled reactions as well as photochemically initiated processes.

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A pyrone remodeling strategy to access diverse heterocycles: application to the synthesis of fascaplysin natural products

Abstract: The synthesis of diverse N-fused heterocycles, including the pyrido[1,2-a]indole scaffold, using an efficient pyrone remodeling strategy is described. The pyrido[1,2-a]indole core was demonstrated to be a versatile scaffold that can be...

Cited by 18 publications

References 63 publications

Unified Total Syntheses of Benzenoid Cephalotane-Type Norditerpenoids: Cephanolides and Ceforalides

Unified Total Syntheses of Benzenoid Cephalotane-Type Norditerpenoids: Cephanolides and Ceforalides

Marine-Derived Lead Fascaplysin: Pharmacological Activity, Total Synthesis, and Structural Modification

Site-Selective Cross-Coupling of Polyhalogenated Arenes and Heteroarenes with Identical Halogen Groups

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