Please use this identifier to cite or link to this item:
http://hdl.handle.net/10261/16967
Share/Export:
![]() ![]() |
|
Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL | DATACITE | |
Title: | Stereospecific synthesis of 1,6-dioxadecalins and 2,2'-linked ditetrahydrofurans by rearrangement of steroidal spiroacetals |
Authors: | Betancor, Carmen; Dorta, Rosa L.; Freire, Raimundo CSIC; Martín, Ángeles CSIC ORCID ; Prangé, Thierry; Suárez, Ernesto CSIC ORCID | Issue Date: | 7-Aug-1998 | Publisher: | American Chemical Society | Citation: | Journal of Organic Chemistry 63(18): 6355-6362 (1998) | Abstract: | The reduction of steroidal spiroacetal methanesulfonate derivatives, containing the 1,6-dioxaspiro[4.5]decan-10-yl ring system, with DIBALH promotes a new rearrangement to give steroidal 1,6-dioxadecalin (octahydropyrano[3,2-b]pyran) or 2,2‘-linked ditetrahydrofuran (octahydro[2,2‘]bifuranyl) derivatives. To study the scope and selectivity of the reaction, several steroidal spiroacetals such as (23R,25R)-3β-methoxy-5α-spirostan-23-yl methanesulfonate (2) and its 23S-isomer (5) and (22R,23R,25R)-3β-acetoxy-16β,23:23,26-diepoxycholest-5-en-22-yl methanesulfonate (15) and its 22S-isomer (19) have been synthesized. Compound 2 was rearranged with absolute regio- and stereoselectivity to give (22S,23S,25R)-3β-methoxy-16β,23:22,26-diepoxy-5α-cholestane (3) which possesses a cis-fused 1,6-dioxadecalin ring system. The reaction of compound 5 gave exclusively (22S,23R,25R)-3β-methoxy-23,26-epoxy-5α-furostane (6) in which the spiroacetal was converted into a ditetrahydrofuran subunit. The two other isomeric spiroacetals 15 and 19 were also mainly transformed into (22S,23S,25R)-3β-acetoxy-16β,23:22,26-diepoxycholest-5-ene (16) and (22R,23R,25R)-3β-acetoxy-23,26-epoxyfurost-5-ene (20), respectively. A mechanism is proposed to explain the regio- and sterospecificity observed in the rearrangement. | Description: | 8 pages, 1 figure, 5 schemes.-- PMID: 11672270 [PubMed].-- Printed version published Sep 4, 1998. Supporting information available at: http://pubs.acs.org/doi/suppl/10.1021/jo980834o |
Publisher version (URL): | http://dx.doi.org/10.1021/jo980834o | URI: | http://hdl.handle.net/10261/16967 | DOI: | 10.1021/jo980834o | ISSN: | 0022-3263 |
Appears in Collections: | (IPNA) Artículos |
Show full item record
Review this work
SCOPUSTM
Citations
22
checked on May 17, 2022
WEB OF SCIENCETM
Citations
21
checked on May 15, 2022
Page view(s)
381
checked on May 19, 2022
Google ScholarTM
Check
Altmetric
Dimensions
WARNING: Items in Digital.CSIC are protected by copyright, with all rights reserved, unless otherwise indicated.