A Short Synthesis of (±)-Epiasarinin

Aldous, David; Dalençon, and Anne J.; Steel, Patrick G.

doi:10.1021/ol025569e

Cited by 34 publications

(10 citation statements)

References 14 publications

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“…Furofurans, such as sesamin, containing the 2,6‐diaryl‐3,7‐dioxabicyclo[3.3.0]octane skeleton, are an important class of natural lignans1 that have shown a wide range of biological activity, such as anti‐tumor, anti‐hypertensive, anti‐inflammatory, insecticidal, and platelet‐activating factor antagonist activity 2–7. Furofurans with a hydroxy group at the bridgehead position, such as gmelinol, have also been found in nature 8–13. It is useful therefore to explore every avenue to aid in the structural elucidation and characterization of such compounds.…”

mentioning

confidence: 99%

Electrospray ionization ion‐trap time‐of‐flight tandem mass spectrometry of two furofurans: sesamin and gmelinol

Yan

Tan

et al. 2007

Rapid Comm Mass Spectrometry

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High-resolution electrospray ionization multistage tandem mass spectrometry (MS(1-7)) in positive ion mode was used to determine the accurate masses and the fragmentation pathways of two furofurans, sesamin and gmelinol. The protonated molecules [M+H]+ were absent in the conventional mass spectra of both compounds, but two characteristic ions, [M+H-H(2)O]+ and [M+H-H(2)]+, were always observed. Successive losses of CH(2)O and CO are the common characteristic fragmentations. Based on the exact masses acquired from 21 different tandem mass spectra, two or three fragmentation pathways for each compound are proposed. The consecutive losses of two H(2)O molecules and one H(2) molecule readily take place from the furan rings for both sesamin and gmelinol, resulting in the absence of the protonated molecules in the single-stage experiments. HCHO loss is observed at least three times in the tandem mass spectra, mainly from methylenedioxy groups (OCH(2)O) for sesamin but only from tetrahydrofuran rings for gmelinol. Moreover, CO loss is found at least three times in the tandem mass spectra of both sesamin and gmelinol from the 3,4-methylenedioxyphenyl (ArOCH(2)O) moieties for sesamin and from both the dimethoxyphenyl and the tetrahydrofuran ring moieties for gmelinol. In addition, the disubstituted benzyl cation ArCH(2)+ at m/z 135 for sesamin and at m/z 151 for gmelinol was found in the MS(3) spectra of both sesamin and gmelinol, which is very helpful in the identification of the compositions of 3,4-disubstituted groups on the benzene rings of the furofurans.

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mentioning

confidence: 99%

Electrospray ionization ion‐trap time‐of‐flight tandem mass spectrometry of two furofurans: sesamin and gmelinol

Yan

Tan

et al. 2007

Rapid Comm Mass Spectrometry

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“…In Steel's report on the short synthesis of Epiasarinin, they used a epoxide-dihydrofuran rearrangement to successfully get the key intermediate 238 (Scheme 131). 178 Interestingly, this reaction is initiated by the cleavage of the C-C bond of the epoxide followed by intramolecular cyclization to give the expected product. Photochemical rearrangement of 2,3-epoxy ketones has also been attempted, which usually gives 3,2-migration products on special epoxy opening at 2-position (Scheme 132).…”

Section: Simple Epoxides and 23-epoxy Ketonesmentioning

confidence: 99%

3.16 The Semipinacol Rearrangements

Wang¹,

Tu²,

Tang³

2014

Comprehensive Organic Synthesis II

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“…In an efficient synthesis of the furofuran (±)-epiasarinin (85), flash vacuum pyrolysis (FVP) of 86, to give dihydropyran 87 in good yield and with high selectivity (cis:trans 8:1), was used as a key step (Scheme 9.35) [154]. The reaction is believed to proceed through conrotatory ring-opening followed by a disrotatory cyclization to give the observed product.…”

Section: Rearrangement Reactionsmentioning

confidence: 99%