Total Synthesis of Amphilectane-Type Diterpenoid (±)-7-Isocyanoamphilecta-11(20),15-diene

Miyaoka, Hiroaki; Okubo, Yusuke

doi:10.1055/s-0030-1259514

Cited by 11 publications

(12 citation statements)

References 40 publications

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“…Therefore, the planning phase for synthesis of polydecalin ICTs should include a careful conformational analysis of the thermodynamically preferred configuration at equilibrium. Some examples benefit from a preference for the targeted stereochemistry upon epimerization ( 96 → 97 , lvi 98 → 99 , lxiii ratios are not given but high selectivity is implied in experimental details). Other cases suffer from the production of inconvenient mixtures ( 100 → 101 , lxiv 102 → 103 ; liv in the latter case, Wood solves this problem in a subsequent step, vide infra ).…”

Section: Chemical Synthesis Of Isocyanoterpenesmentioning

confidence: 99%

Syntheses and biological studies of marine terpenoids derived from inorganic cyanide

Schnermann

Shenvi

2015

Nat. Prod. Rep.

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Isocyanoterpenes (ICTs) are marine natural products biosynthesized through an unusual pathway that adorns terpene scaffolds with nitrogenous functionality derived from cyanide. The appendage of nitrogen functional groups–isonitriles in particular–onto stereochemically-rich carbocyclic ring systems provides enigmatic, bioactive molecules that have required innovative chemical syntheses. This review discusses the challenges inherent to the synthesis of this diverse family and details the development of the field. We also present recent progress in isolation and discuss key aspects of the remarkable biological activity of these compounds.

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Section: Chemical Synthesis Of Isocyanoterpenesmentioning

confidence: 99%

Syntheses and biological studies of marine terpenoids derived from inorganic cyanide

Schnermann

Shenvi

2015

Nat. Prod. Rep.

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“…The carbons in compound 1 were numbered according to the precedent pseudopterosins [ 11 ]. The structure of 1 is recognized as a new amphilectane-type diterpenoid [ 12 , 13 ], and the name acrepseudoterin is proposed for compound 1 .…”

Section: Resultsmentioning

confidence: 99%

PTP1B Inhibitory Secondary Metabolites from an Antarctic Fungal Strain Acremonium sp. SF-7394

Kim

et al. 2021

Molecules

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Chemical investigation of the Antarctic lichen-derived fungal strain Acremonium sp. SF-7394 yielded a new amphilectane-type diterpene, acrepseudoterin (1), and a new acorane-type sesquiterpene glycoside, isocordycepoloside A (2). In addition, three known fungal metabolites, (−)-ternatin (3), [D-Leu]-ternatin (4), and pseurotin A (5), were isolated from the EtOAc extract of the fungal strain. Their structures were mainly elucidated by analyzing their NMR and MS data. The absolute configuration of 1 was proposed by electronic circular dichroism calculations, and the absolute configuration of the sugar unit in 2 was determined by a chemical method. The inhibitory effects of the isolated compounds on protein tyrosine phosphatase 1B (PTP1B) were evaluated by enzymatic assays; results indicated that acrepseudoterin (1) and [D-Leu]-ternatin (4) dose-dependently inhibited the enzyme activity with IC50 values of 22.8 ± 1.1 μM and 14.8 ± 0.3 μM, respectively. Moreover, compound 1 was identified as a competitive inhibitor of PTP1B.

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“…In 2011, Miyaoka and co‐workers disclosed a formal synthesis of DICA, reaching the Corey dione through a sequence that is strategically aligned with the Corey and Magriotis accomplishment but somewhat lengthier . Piers and co‐workers completed syntheses of amphilectane and cycloamphilectane ICTs with isonitriles located at ring junctions, and Miyaoka and Okubo made an amphilectane natural product related to 3 . Finally, the stunning 2014 synthesis of (±)‐amphilectene 3 by Pronin and Shenvi in approximately 10 steps raised the bar for synthesis in this area; moreover, they introduced an important tool for stereocontrolled introduction of the tertiary isonitriles, namely a largely invertive displacement of tertiary trifluoroacetates …”

Section: Figurementioning

confidence: 99%

A Formal Enantiospecific Synthesis of 7,20‐Diisocyanoadociane

Roosen

Vanderwal

2016

Angewandte Chemie

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7,20‐Diisocyanoadociane (DICA) is a potent antimalarial isocyanoterpene endowed with a fascinating tetracyclic structure composed of fused chair cyclohexanes. We report a highly stereocontrolled synthesis of a late‐stage intermediate, the “Corey dione”, from which DICA has been made previously. This formal synthesis features a rapid buildup of much of the complexity of the target through a sequence of enone tandem vicinal difunctionalization, Friedel–Crafts cyclodehydration, and sequential stereocontrolled reductions. Most importantly, this success establishes the broader feasibility of our previously developed general synthesis approach to the isocyanoterpene family and provides a blueprint for a very direct synthesis of DICA and related natural products.

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Total Synthesis of Amphilectane-Type Diterpenoid (±)-7-Isocyanoamphilecta-11(20),15-diene

Cited by 11 publications

References 40 publications

Syntheses and biological studies of marine terpenoids derived from inorganic cyanide

Syntheses and biological studies of marine terpenoids derived from inorganic cyanide

PTP1B Inhibitory Secondary Metabolites from an Antarctic Fungal Strain Acremonium sp. SF-7394

A Formal Enantiospecific Synthesis of 7,20‐Diisocyanoadociane

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