Cycloaddition of allylsilanes. Part 20: Organosilicon-mediated total synthesis of (±)-cameroonanol

Schmidt, Arndt W.; Olpp, T.; Schmid, Sören; Jäger, Anne; Knölker, Hans‐Joachim

doi:10.1016/j.tet.2009.01.115

Cited by 10 publications

(7 citation statements)

References 50 publications

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“…175 A new caryolane sesquiterpene 173 has been isolated from cultures of the basidiomycete Campanella junghuhnii. 176 A racemic synthesis of cameroonanol has been described, 177 whilst the total synthesis of (À)-penifulvin A 174 has been achieved. This insecticidal sesquiterpene possesses a seco-silphinane skeleton.…”

Section: Chamigrane and Widdranementioning

confidence: 99%

Natural sesquiterpenoids

Fraga

2010

Nat. Prod. Rep.

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Section: Chamigrane and Widdranementioning

confidence: 99%

Natural sesquiterpenoids

Fraga

2010

Nat. Prod. Rep.

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“…As confirmed by GC-MS and TLC analyses, BF 3 -catalyzed rearrangement indeed gave cameroonanone exclusively. The NMR data of 2a were in excellent agreement with those previously reported . Analogously to 1a , its epimer 1b should rearrange to 9- epi -cameroonanone, which could be easily distinguished from cameroonanone .…”

Section: Results and Discussionmentioning

confidence: 61%

“…One should expect 1a to preferably rearrange to 2a and not 2c , since 2a is energetically more favorable; 2c contains a strained four-membered ring, condensed to a bicyclic core. Upon Lewis acid treatment, the title compound is expected to convert to the known product cameroonanone ( 2a ) . As confirmed by GC-MS and TLC analyses, BF 3 -catalyzed rearrangement indeed gave cameroonanone exclusively.…”

Section: Results and Discussionmentioning

confidence: 99%

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Structural Elucidation of Presilphiperfolane-7α,8α-diol, a Bioactive Sesquiterpenoid from Pulicaria vulgaris: A Combined Approach of Solvent-Induced Chemical Shifts, GIAO Calculation of Chemical Shifts, and Full Spin Analysis

et al. 2019

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Structural elucidation of a new triquinane sesquiterpenoid, presilphiperfolane-7α,8α-diol, 1a, isolated from Pulicaria vulgaris, was accomplished by combining solvent-induced removal of chemical shift degeneracy and computational (DFT-GIAO) prediction of NMR spectra with the analysis of 1H NMR splitting patterns. In addition to extensive NMR experiments (in 10 different solvents), MS, and FTIR, the identity of 1a was also confirmed by chemical transformations. The applied approach can facilitate structural elucidation of organic molecules and decrease the probability of an erroneous identification, permitting an unambiguous stereochemical elucidation and full NMR assignment. The pharmacological/toxicological profile of 1a was evaluated in several different models.

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“…After its isolation and identification by Weyerstahl et al, Coates et al reported the first total synthesis by using the Sakurai reaction as a key step starting with bicyclic enone . Later, Knölker et al described the total synthesis by a slightly modified procedure from the same bicyclic enone via [3 + 2] cycloaddition . However, the enantiopure (−)-cameroonan-7α-ol synthesis was reported by Nelson et al starting with (+)-citronellal (21 steps) .…”

Section: Introductionmentioning

confidence: 99%

A Modular Approach to Angularly Fused Polyquinanes via Ring-Rearrangement Metathesis: Synthetic Access to Cameroonanol Analogues and the Basic Core of Subergorgic Acid and Crinipellin

Kotha

Keesari

2021

J. Org. Chem.

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We describe a modular approach to angularly fused polyquinanes that are core units of many natural products such as cameroonanol, subergorgic acid, and crinepellin, etc. in excellent yields by employing atom-economic ring-rearrangement metathesis as a key step. Our work highlights, the synthesis of cameroonanol analogues 1–6 and their ester derivatives by using the stereoselective reduction of the carbonyl group by using DIBAL-H- and DCC-mediated coupling as the key reactions. The subergorgic acid core 7 was produced by LDA-mediated kinetically controlled regio- and stereoselective ring-junction allylation as a critical step. Moreover, it is worth mentioning that the present strategy relies on a less explored exo-dicyclopentadiene-1-one (8) and produces highly congested polycyclic frameworks containing up to seven contiguous stereogenic centers including quaternary carbons up to two. All of the new molecules were characterized by NMR data. The structure and relative stereochemistry of some compounds were confirmed by chemical methods and further supported by single-crystal X-ray diffraction studies. The newly reported tri- and tetraquinane skeletons are present in many naturally occurring bioactive polyquinanes. Hence, this strategy is useful for designing various “druglike molecules” and expands the chemical space of cyclopentanoids that are useful in medicinal chemistry.

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Cycloaddition of allylsilanes. Part 20: Organosilicon-mediated total synthesis of (±)-cameroonanol

Cited by 10 publications

References 50 publications

Natural sesquiterpenoids

Natural sesquiterpenoids

Structural Elucidation of Presilphiperfolane-7α,8α-diol, a Bioactive Sesquiterpenoid from Pulicaria vulgaris: A Combined Approach of Solvent-Induced Chemical Shifts, GIAO Calculation of Chemical Shifts, and Full Spin Analysis

A Modular Approach to Angularly Fused Polyquinanes via Ring-Rearrangement Metathesis: Synthetic Access to Cameroonanol Analogues and the Basic Core of Subergorgic Acid and Crinipellin

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