dc.creator | Quindt, Matías Iván | |
dc.creator | Gola, Gabriel Francisco | |
dc.creator | Ramirez, Javier Alberto | |
dc.creator | Bonesi, Sergio Mauricio | |
dc.date.accessioned | 2021-10-06T21:30:09Z | |
dc.date.accessioned | 2022-10-15T03:18:24Z | |
dc.date.available | 2021-10-06T21:30:09Z | |
dc.date.available | 2022-10-15T03:18:24Z | |
dc.date.created | 2021-10-06T21:30:09Z | |
dc.date.issued | 2019-05 | |
dc.identifier | Quindt, Matías Iván; Gola, Gabriel Francisco; Ramirez, Javier Alberto; Bonesi, Sergio Mauricio; Photo-Fries Rearrangement of Some 3‑Acylestrones in Homogeneous Media: Preparative and Mechanistic Studies; American Chemical Society; Journal of Organic Chemistry; 84; 5-2019; 7051-7065 | |
dc.identifier | 0022-3263 | |
dc.identifier | http://hdl.handle.net/11336/142989 | |
dc.identifier | CONICET Digital | |
dc.identifier | CONICET | |
dc.identifier.uri | https://repositorioslatinoamericanos.uchile.cl/handle/2250/4339268 | |
dc.description.abstract | 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. | |
dc.language | eng | |
dc.publisher | American Chemical Society | |
dc.relation | info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.joc.9b00786 | |
dc.relation | info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/acs.joc.9b00786 | |
dc.rights | https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ | |
dc.rights | info:eu-repo/semantics/restrictedAccess | |
dc.subject | Photo-Fries | |
dc.subject | Norrish | |
dc.subject | Estrone | |
dc.subject | Photorearrangement | |
dc.title | Photo-Fries Rearrangement of Some 3‑Acylestrones in Homogeneous Media: Preparative and Mechanistic Studies | |
dc.type | info:eu-repo/semantics/article | |
dc.type | info:ar-repo/semantics/artículo | |
dc.type | info:eu-repo/semantics/publishedVersion | |