A Biomimetic Synthesis of Sacculatane Diterpenoids

Grinco, Marina; Kulciţki, Veaceslav; Ungur, Nicon; Vlad, P. F.; Gavagnin, Margherita; Castelluccio, Francesco; Cimino, Guido

doi:10.1002/hlca.200890031

Cited by 4 publications

(1 citation statement)

References 14 publications

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“…The biomimetic synthesis of the sacculatanic skeleton was reported in a single publication and it was based on the superacidic cyclization of an a,u-bifunctional diterpenic substrate. 176 efforts, since direct allylic oxidation of geranylgeraniol derivatives with selenium dioxide was not feasible. Therefore, the introduction of the terminal oxygenated functional group required a long sequence of transformations, starting from geranyllinalool 274 (Scheme 15).…”

Section: Synthetic Approaches Towards Natural Products With Terminal ...mentioning

confidence: 99%

Unusual cyclic terpenoids with terminal pendant prenyl moieties: from occurrence to synthesis

2014

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The paper reviews the known examples of cyclic terpenoids produced from open chain polyenic precursors by an "unusual" biosynthetic pathway, involving selective electrophilic attack on an internal double bond followed by cyclization. The resulting compounds possess cyclic backbones with pendant terminal prenyl groups. Synthetic approaches applied for the synthesis of such specifically functionalized compounds are also discussed, as well as biological activity of reported representatives.

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Section: Synthetic Approaches Towards Natural Products With Terminal ...mentioning

confidence: 99%

Unusual cyclic terpenoids with terminal pendant prenyl moieties: from occurrence to synthesis

2014

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Synthesis of Natural Atisane‐Type Diterpenoids by retro‐Biomimetic Transformations

Ungur

Kulciţki

Chetraru

et al. 2013

Helvetica Chimica Acta

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An efficient one step, retro-biomimetic procedure for the synthesis of natural products having the atisane structure is described (Scheme 2), natural products which are components of medicinal plants and possess relevant biological activity. Their structures were confirmed by chemical transformations and spectral data. The starting materials were the known ent-kaur-16-en-19-oic acid (1) and ent-trachyloban-19-oic acid (2), diterpenoids readily available from the waste of sunflower.Introduction. -Tetracyclic atisanes, beyeranes, kauranes, and pentacyclic trachylobanes represent an important group of biosynthetically closely related polycyclic diterpenes, many of which display a wide range of biological activities [1 -7]. According to the hypothesis of diterpene biogenesis [8], diterpenes belonging to the families of ent-beyerene (A), ent-kaurene (B), ent-trachylobane (C), and ent-atisene (D) might all arise from (À)-copalyl pyrophosphate E via nonclassical carbocations such as F as common intermediates (Scheme 1). This hypothesis [8] has been formulated on the basis of the known isoprene rule and, to the best of our knowledge, has not been turned down yet. Scheme 1 provides a general overview of this biogenetic scheme, and our primary intention was to perform the retro-biomimetic transformation of ent-kaurene (B) to ent-beyerene (A) or ent-atisene (D) (path B ! F ! A or D).The rearrangements of ent-kaurane-and ent-trachylobane-type diterpenes have been reported under the action of different reagents [9]. Most of the examples relate on the reactions involving the formation of the nonclassical carbocation of type F (Scheme 1). It is well-known from the work of Olah and co-workers [10] that superacids are very convenient generators of these species, and our own experience on the use of fluorosulfuric acid (¼ fluorosulfonic acid; FSO 3 H) as an efficient promoter of terpenoid cyclizations [11 -15] and rearrangements [16 -18] provided a motivation to investigate the behavior of ent-kaur-16-en-19-oic acid (1) [19] and ent-trachyloban-19-oic acid (2) under superacid treatment (Scheme 2).

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Target-Oriented Synthesis of Some Terpenoids of Marine Origin

Ungur¹

2011

ChemJMold

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A Biomimetic Synthesis of Sacculatane Diterpenoids

Cited by 4 publications

References 14 publications

Unusual cyclic terpenoids with terminal pendant prenyl moieties: from occurrence to synthesis

Unusual cyclic terpenoids with terminal pendant prenyl moieties: from occurrence to synthesis

Synthesis of Natural Atisane‐Type Diterpenoids by retro‐Biomimetic Transformations

Target-Oriented Synthesis of Some Terpenoids of Marine Origin

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