Synthesis of halo-fluoro-substituted adamantanes by electrophilic transannular cyclization of bicyclo[3.3.1]nonane dienes

Graphic 3,7-Dimethylenebicyclo[3.3.1]nonane and its derivatives with a methyl or phenyl substituent in a methylene group react, with N-halosuccinimides NXS (X=Cl, Br, I) in dichloromethane in the presence of tetrabutylammonium dihydrotrifluoride or polyfluorinated alcohols via a transannular cycliza...

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Bibliographic Details
Published in:Journal of fluorine chemistry 2003-10, Vol.123 (2), p.207-215
Main Authors: Serguchev, Yurii A, Ponomarenko, Maxim V, Lourie, Lyudmila F, Chernega, Alexander N
Format: Article
Language:English
Subjects:
Adamantane derivatives
Dienes of bicyclo[3.3.1]nonane series
Halofluorination
Transannular cyclization
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Summary:Graphic 3,7-Dimethylenebicyclo[3.3.1]nonane and its derivatives with a methyl or phenyl substituent in a methylene group react, with N-halosuccinimides NXS (X=Cl, Br, I) in dichloromethane in the presence of tetrabutylammonium dihydrotrifluoride or polyfluorinated alcohols via a transannular cyclization leading to the corresponding 1-fluoro- or 1-polyfluoroalkoxy-3-halomethyladamantanes. The reaction of the dienes with NXS and Bu 4N +H 2F 3 − conducted in THF, oxetane or ethylene oxide runs through a cascade addition of electrophiles (positively charged halogen atoms) and external nucleophiles (solvent molecules and halide anions) to the starting diene substrate and intermediate adamantyl carbocation.
ISSN:0022-1139
1873-3328
DOI:10.1016/S0022-1139(03)00135-0