Revisiting the bromination of 3β-hydroxycholest-5-ene with CBr4/PPh3 and the subsequent azidolysis of the resulting bromide, disparity in stereochemical behavior
Schumacher, C., Ward, J. S., Rissanen, K., Bolm, C., & Ramadan El Sayed Aly, M. (2023). Revisiting the bromination of 3β-hydroxycholest-5-ene with CBr4/PPh3 and the subsequent azidolysis of the resulting bromide, disparity in stereochemical behavior. Beilstein Journal of Organic Chemistry, 19, 91-99. https://doi.org/10.3762/bjoc.19.9
Julkaistu sarjassa
Beilstein Journal of Organic ChemistryTekijät
Päivämäärä
2023Tekijänoikeudet
© Authors 2023
Cholesterol reacts under Appel conditions (CBr4/PPh3) to give 3,5-cholestadiene (elimination) and 3β-bromocholest-5-ene (substitution with retention of configuration). Thus, the bromination of cholesterol deviates from the stereochemistry of the standard Appel mechanism due to participation of the Δ5 π-electrons. In contrast, the subsequent azidolysis (NaN3/DMF) of 3β-bromocholest-5-ene proceeds predominantly by Walden inversion (SN2) affording 3α-azidocholest-5-ene. The structures of all relevant products were revealed by X-ray single crystal structure analyses, and the NMR data are in agreement to the reported ones. In light of these findings, we herein correct the previous stereochemical assignments reported by one of us in the Beilstein J. Org. Chem. 2015, 11, 1922–1932 and the Monatsh. Chem. 2018, 149, 505–517.
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Beilstein InstitutISSN Hae Julkaisufoorumista
2195-951XAsiasanat
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https://converis.jyu.fi/converis/portal/detail/Publication/176612384
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We are grateful to the Alexander von Humboldt Foundation and the Verband der Chemischen Industrie e.V. for support of K. R. (AvH research award) and C. S. (Kekulé scholarship), respectively. The support of Port Said University is kindly acknowledged.Lisenssi
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