Unnaturally configured 13‐epi steroids: full 1H and 13C assignments and ring C–D conformations from 1H, 1H vicinal couplings

Fielding, Lee A.; Diepeveen, Yolande; Fletcher, Dan; Hamilton, Niall M.

doi:10.1002/mrc.853

Cited by 7 publications

(3 citation statements)

References 42 publications

(37 reference statements)

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“…Analysis of the purified product by 1 H-NMR spectroscopy confirms its identity as lumiestrone; the chemical shifts for the protons of the purified product match those assigned to lumiestrone in a detailed NMR analysis of unnatural 13-epi steroids (Fielding et al, 2001). Fig.…”

Section: Characterization Of Lumiestronementioning

confidence: 53%

Photochemical induced changes of in vitro estrogenic activity of steroid hormones

et al. 2012

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Section: Characterization Of Lumiestronementioning

confidence: 53%

Photochemical induced changes of in vitro estrogenic activity of steroid hormones

et al. 2012

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“…White needles (0.018 g, 12%). mp: 268–269 °C (268–269 °C). 1 H NMR (500 MHz): δ 7.15 (dd, J = 8.5, 1.0 Hz, 1H), 6.64 (dd, J = 8.4, 2.8 Hz, 1H), 6.59 (d, J = 2.8 Hz, 1H), 2.79 (d, J = 8.2 Hz, 2H, H-6 and H-6′), 1.05 (s, 3H, H-18), 1.00–0.95 (m, 1H, H-11).…”

Section: Methodsmentioning

confidence: 99%

Photo-Fries Rearrangement of Some 3-Acylestrones in Homogeneous Media: Preparative and Mechanistic Studies

et al. 2019

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Irradiation of a series of 3-acylestrones under a nitrogen atmosphere in cyclohexane, acetonitrile (MeCN), and methanol (MeOH) was investigated under steady-state conditions. The molecules underwent the photo-Fries rearrangement, with concomitant homolytic fragmentation of the ester group and [1;3]-acyl migration. This pathway afforded the ortho-acyl estrone derivatives, the main photoproducts, together with estrone. During the irradiation of 3-benzoyl estrone, epimerization of estrone through the Norrish type I reaction occurred, providing lumiestrone as the photoproduct. This photoreaction involves the fragmentation of the C-α at the carbonyl group (C-17) of the steroid. On the other hand, epimerization of ortho-regioisomer 2-acetyl estrone occurred during the irradiation of 3-acetyl estrone. Photosensitization with acetone and chemical quenching with N,N,N,N-tetramethyldiazetinedioxide of the photo-Fries reaction confirmed that the photoreaction took place from the singlet excited state while the Norrish type I reaction proceeds efficiently from the triplet excited state. Solvent effects, as well as the nature of the acyl group on the photoreactions, were also studied.

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“…Lumiestrone was obtained as a pure product after 17 min using an isocratic elution with 70% acetonitrile and 30% water and a flow of 10 mL/min. Lumiestrone was then characterized by nuclear magnetic resonance spectroscopy (NMR; Fielding et al, 2001 ). NMR spectra were recorded at 400 MHz for [ 1 H] and 100 MHz for [ 13 C] on a Bruker Avance 400 spectrometer.…”

Section: Methodsmentioning

confidence: 99%

Lumiestrone is Photochemically Derived from Estrone and may be Released to the Environment without Detection

Trudeau¹,

Heyne²,

Blais³

et al. 2011

Front. Endocrin.

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Endocrine disrupting chemicals are adversely affecting the reproductive health and metabolic status of aquatic vertebrates. Estrone is often the dominant natural estrogen in urban sewage, yet little is known about its environmental fate and biological effects. Increased use of UV-B radiation for effluent treatments, and exposure of effluents to sunlight in holding ponds led us to examine the effects of environmentally relevant levels of UV-B radiation on the photodegradation potential of estrone. Surprisingly, UV-B-mediated degradation leads to the photoproduction of lumiestrone, a little known 13α-epimer form of estrone. We show for the first time that lumiestrone possesses novel biological activity. In vivo treatment with estrone stimulated estrogen receptor (ER) α mRNA production in the male goldfish liver, whereas lumiestrone was without effect, suggesting a total loss of estrogenicity. In contrast, results from in vitro ER-dependent reporter gene assays indicate that lumiestrone showed relatively higher estrogenic potency with the zebrafish ERβ2 than zfERα, suggesting that it may act through an ERβ-selectivity. Lumiestrone also activated human ERs. Microarray analysis of male goldfish liver following in vivo treatments showed that lumiestrone respectively up- and down-regulated 20 and 69 mRNAs, which was indicative of metabolic upsets and endocrine activities. As a photodegradation product from a common estrogen of both human and farm animal origin, lumiestrone is present in sewage effluent, is produced from estrone upon exposure to natural sunlight and should be considered as a new environmental contaminant.

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Unnaturally configured 13‐epi steroids: full ¹H and ¹³C assignments and ring C–D conformations from ¹H, ¹H vicinal couplings

Cited by 7 publications

References 42 publications

Photochemical induced changes of in vitro estrogenic activity of steroid hormones

Photochemical induced changes of in vitro estrogenic activity of steroid hormones

Photo-Fries Rearrangement of Some 3-Acylestrones in Homogeneous Media: Preparative and Mechanistic Studies

Lumiestrone is Photochemically Derived from Estrone and may be Released to the Environment without Detection

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