Unified Total Synthesis of Diverse Meroterpenoids from <i>Ganoderma Applanatum</i>

Šimek, M.; Bártová, Kateřina; Issad, Samy; Hájek, Miroslav; Cı́sařová, Ivana; Jahn, Ullrich

doi:10.1021/acs.orglett.2c01633

Cited by 19 publications

(9 citation statements)

References 29 publications

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“…29 Absolute configuration elucidations of these racemates were accomplished by ECD calculations and CD comparisons, and the relative configurations of (±)-applanatumol V (141 and 142) were revised by using synthesis methods. 66 Unusual enantiomers of (±)-applanatumol B (156 and 157) possessing a dioxacyclopenta[cd]inden motif were characterized by spectroscopic methods and ECD calculations. 67 In terms of biosynthetic pathway, the precursor of applanatumol B may be a derivative of applanatumol V (141 and 142) (Supporting Information: Scheme S1).…”

Section: F I G U R E 6 Structures Of Ganoderma Meroterpenoid Alkaloidsmentioning

confidence: 99%

“…136 And in 2022, the Jahn group achieved applanatumols B, X and Y in 13 and 10 steps, respectively, and reported the first total syntheses of applanatumol V (141) in 10 steps and applanatumol W (143) in 11 steps. 66 The Qin and Liu group described the first total synthesis of (±)-cochlearol A (164 and 165) in 16 steps, relying on a TMSOTf-catalyzed lactonization of tert-butyl ether and ethyl ester. 137 Later, in 2020, Ishigami et al reported their syntheses approach of (±)-cochlearol A (164 and 165) via an intramolecular acetal reaction of a key spiroepoxide intermediate.…”

Section: The Total Synthesis Of Gmsmentioning

confidence: 99%

“…cochlear 29 . Absolute configuration elucidations of these racemates were accomplished by ECD calculations and CD comparisons, and the relative configurations of (±)‐applanatumol V ( 141 and 142 ) were revised by using synthesis methods 66 …”

Section: Meroterpenoids From Ganoderma and Their Biological Activitiesmentioning

confidence: 99%

“…Applanatumol B ( 156 ) was first totally synthesized by Ito et al in 14 steps in 2019, and then the Ito group developed the first total syntheses of applanatumol X ( 147 ) in 9 steps and applanatumol Y ( 149 ) in 10 steps, relying on the same key intermediate in the synthesis of applanatumol B 136 . And in 2022, the Jahn group achieved applanatumols B, X and Y in 13 and 10 steps, respectively, and reported the first total syntheses of applanatumol V ( 141 ) in 10 steps and applanatumol W ( 143 ) in 11 steps 66 …”

Section: The Total Synthesis Of Gmsmentioning

confidence: 99%

See 3 more Smart Citations

Insights into Ganoderma fungi meroterpenoids opening a new era of racemic natural products in mushrooms

Zhang,

Qin,

Cheng

2024

Medicinal Research Reviews

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Ganoderma meroterpenoids (GMs) containing 688 structures to date were discovered to have multiple remarkable biological activities. 65.6% of meroterpenoids featuring stereogenic centers from Ganoderma species are racemates. Further, GMs from different Ganoderma species seem to have their own characteristics. In this review, a comprehensive summarization of GMs since 2000 is presented, including GM structures, structure corrections, biological activities, physicochemical properties, total synthesis, and proposed biosynthetic pathways. Additionally, we especially discuss the racemic nature, species‐related structural distribution, and structure–activity relationship of GMs, which will provide a likely in‐house database and shed light on future studies on GMs.

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Section: F I G U R E 6 Structures Of Ganoderma Meroterpenoid Alkaloidsmentioning

confidence: 99%

Section: The Total Synthesis Of Gmsmentioning

confidence: 99%

Section: Meroterpenoids From Ganoderma and Their Biological Activitiesmentioning

confidence: 99%

Section: The Total Synthesis Of Gmsmentioning

confidence: 99%

See 2 more Smart Citations

Insights into Ganoderma fungi meroterpenoids opening a new era of racemic natural products in mushrooms

Zhang,

Qin,

Cheng

2024

Medicinal Research Reviews

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“…1366 Applying this strategy, interesting scaffolds could be constructed, and applications in the total synthesis of diverse meroterpenoids were presented (Scheme 89a). 1367 For example, with tetraallyltin, an allyl group was added to the dienone 291, and warming of the reaction mixture induced an oxy-Cope rearrangement of intermediate 292 to give a keto enolate, which was SET oxidized and trapped by TEMPO to give the alkoxyamine 293. Under reflux condition, alkoxyamine isomerization comprising a 5-exo-cyclization was achieved to give 294.…”

Section: Reactions Of Alkoxyaminesmentioning

confidence: 99%

Organic Synthesis Using Nitroxides

Leifert

Studer

2023

Chem. Rev.

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Nitroxides, also known as nitroxyl radicals, are long-lived or stable radicals with the general structure R 1 R 2 N−O • . The spin distribution over the nitroxide N and O atoms contributes to the thermodynamic stability of these radicals. The presence of bulky N-substituents R 1 and R 2 prevents nitroxide radical dimerization, ensuring their kinetic stability. Despite their reactivity toward various transient C radicals, some nitroxides can be easily stored under air at room temperature. Furthermore, nitroxides can be oxidized to oxoammonium salts (R 1 R 2 N�O + ) or reduced to anions (R 1 R 2 N−O − ), enabling them to act as valuable oxidants or reductants depending on their oxidation state. Therefore, they exhibit interesting reactivity across all three oxidation states. Due to these fascinating properties, nitroxides find extensive applications in diverse fields such as biochemistry, medicinal chemistry, materials science, and organic synthesis. This review focuses on the versatile applications of nitroxides in organic synthesis. For their use in other important fields, we will refer to several review articles. The introductory part provides a brief overview of the history of nitroxide chemistry. Subsequently, the key methods for preparing nitroxides are discussed, followed by an examination of their structural diversity and physical properties. The main portion of this review is dedicated to oxidation reactions, wherein parent nitroxides or their corresponding oxoammonium salts serve as active species. It will be demonstrated that various functional groups (such as alcohols, amines, enolates, and alkanes among others) can be efficiently oxidized. These oxidations can be carried out using nitroxides as catalysts in combination with various stoichiometric terminal oxidants. By reducing nitroxides to their corresponding anions, they become effective reducing reagents with intriguing applications in organic synthesis. Nitroxides possess the ability to selectively react with transient radicals, making them useful for terminating radical cascade reactions by forming alkoxyamines. Depending on their structure, alkoxyamines exhibit weak C−O bonds, allowing for the thermal generation of C radicals through reversible C−O bond cleavage. Such thermally generated C radicals can participate in various radical transformations, as discussed toward the end of this review. Furthermore, the application of this strategy in natural product synthesis will be presented.

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Total Synthesis of Ganoderma Meroterpenoids – Progresses since 2014

Kawamoto,

Ito

2024

Asian J Org Chem

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Meroterpenoids isolated from fungi of the Ganoderma family have received much attention owing to their unique structures and diverse biological activities. A number of Ganoderma meroterpenoids have been isolated since 2000 and many total syntheses and synthetic studies have since been reported. In this review, we highlight fifteen total syntheses conducted from 2014 to 2023 of polycyclic Ganoderma meroterpenoids classified according to the connection pattern of the dihydroquinone with the terpenoid structure. The selected studies illustrate how the molecular complexity was constructed by unique tactics.

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Unified Total Synthesis of Diverse Meroterpenoids from Ganoderma Applanatum

Cited by 19 publications

References 29 publications

Insights into Ganoderma fungi meroterpenoids opening a new era of racemic natural products in mushrooms

Insights into Ganoderma fungi meroterpenoids opening a new era of racemic natural products in mushrooms

Organic Synthesis Using Nitroxides

Total Synthesis of Ganoderma Meroterpenoids – Progresses since 2014

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