Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/17238
Share/Export:
logo share SHARE logo core CORE BASE
Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL | DATACITE
Title

Tandem Carbon-Radical Peroxidation-Addition to Carbonyl Groups Reaction. A New Synthesis of Steroidal β-Peroxy Lactones

AuthorsBoto, Alicia CSIC ORCID ; Hernández, Rosendo CSIC; Suárez, Ernesto CSIC ORCID; Betancor, Carmen; Rodríguez Morales, María S. CSIC ORCID
Issue DateDec-1995
PublisherAmerican Chemical Society
CitationJournal of Organic Chemistry 60(25): 8209-8217 (1995)
AbstractA mild and efficient synthesis of β-peroxy lactones by alkoxy radical β-fragmentation reaction of γ-hydroxy carbonyl compounds is described. Steroidal models 5-hydroxy-4-nor-3-oxa-5α-cholestan-2-one (1), 5-hydroxy-5α-cholestan-2-one (2), and 5,17β-dihydroxy-4-nor-5α-androstan-2-one 17-acetate (3) were synthesized to test the present methodology. These substrates are subjected to photolysis with visible light in the presence of (diacetoxyiodo)benzene, lead tetraacetate, or HgO, I2, and molecular oxygen to generate the corresponding alkoxy radical. The fragmentation of this radical results in the carbon radical which is trapped by molecular oxygen in the key step to generate a peroxy radical. Intramolecular addition of this peroxy radical to the carbonyl group present in the molecule is followed by β-fragmentation to yield the peroxy ladone radical. Subsequent trapping of this radical results in stable peroxy lactone. In all cases, regiospecific β-fragmentations and stereoselective peroxidation at C-10 radical were observed. This operationally simple multistep radical procedure permitted us to synthesize steroidal β-peroxy lactones 8, 12, and 15 in moderate to good yields.
Description9 pages, 1 table, 7 schemes.-- Supporting information available at: http://pubs.acs.org/doi/suppl/10.1021/jo00130a020
Publisher version (URL)http://dx.doi.org/10.1021/jo00130a020
URIhttp://hdl.handle.net/10261/17238
DOI10.1021/jo00130a020
ISSN0022-3263
Appears in Collections:(IPNA) Artículos

Show full item record
Review this work

SCOPUSTM   
Citations

13
checked on May 11, 2022

WEB OF SCIENCETM
Citations

12
checked on May 13, 2022

Page view(s)

343
checked on May 18, 2022

Google ScholarTM

Check

Altmetric

Dimensions


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