Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/17241
Share/Export:
logo share SHARE logo core CORE BASE
Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL | DATACITE
Title

Tandem β-fragmentation-hydrogen abstraction reaction of alkoxy radicals in steroidal systems

AuthorsBoto, Alicia CSIC ORCID ; Freire, Raimundo CSIC; Hernández, Rosendo CSIC; Suárez, Ernesto CSIC ORCID
Issue Date2-May-1997
PublisherAmerican Chemical Society
CitationJournal of Organic Chemistry 62(9): 2975-2981 (1997)
AbstractA number of tertiary or hemiacetalic steroidal alcohols, 2-hydroxy-3,4-dinor-2,3-secocholestan-5-one 2,5-hemiacetal (1), 2β,3β-dihydro-3'H-cyclopropa[2,3]-cholestan-5α-ol (7), 3β-phenyl-5α-hydroxycholestan-2-one (10), 5α-hydroxycholestan-3-one (15), 3β,5α-dihydroxycholestan-7-one 3-acetate (21), and 4,4-dimethyl-19-hydroxy-5α-cholestan-3-one 19,3-hemiacetal (27) have been prepared in order to test a new tandem β-fragmentation−hydrogen abstraction reaction. The alkoxy radicals generated by irradiation of these alcohols with visible light in the presence of (diacetoxyiodo)benzene, iodine, and molecular oxygen undergo a β-fragmentation reaction followed by peroxidation of the C-radical formed. The peroxy radical reacts further with iodine to give an alkoxy radical and iodoxyl radical (IO•). The new alkoxy radical can produce intramolecular functionalization of suitably positioned carbons by hydrogen abstraction through a six-membered cyclic transition state to give tetrahydrofurans or can be intramolecularly trapped by carbonyl groups suitably disposed so as to generate a new alkoxy radical that can afford γ-lactones by β-fragmentation.
Description7 pages, 1 table, 11 schemes.-- PMID: 11671662 [PubMed].-- Supporting information available at: http://pubs.acs.org/doi/suppl/10.1021/jo962252h
Publisher version (URL)http://dx.doi.org/10.1021/jo962252h
URIhttp://hdl.handle.net/10261/17241
DOI10.1021/jo962252h
ISSN0022-3263
Appears in Collections:(IPNA) Artículos

Show full item record
Review this work

SCOPUSTM   
Citations

25
checked on Jul 5, 2022

WEB OF SCIENCETM
Citations

20
checked on Jul 5, 2022

Page view(s)

294
checked on Jul 4, 2022

Google ScholarTM

Check

Altmetric

Dimensions


WARNING: Items in Digital.CSIC are protected by copyright, with all rights reserved, unless otherwise indicated.