Straightforward synthesis of a vicinal double bridgehead iodo trimethylsilyl octacycle: unprecedented lack of reactivity of the silyl group in front of fluoride anions.
Abstract: A convenient synthesis of an octacyclic compound containing an iodo and a trimethylsilyl group in vicinal double bridgehead positions, as a possible precursor of a pyramidalized alkene, is described. The key step of the synthesis consists of a double nucleophilic substitution of two neopen...
| Authors: | , , , , , , |
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| Format: | article |
| Status: | Versión aceptada para publicación |
| Publication Date: | 2017 |
| Country: | España |
| Institution: | Universidad de Barcelona |
| Repository: | Dipòsit Digital de la UB |
| OAI Identifier: | oai:diposit.ub.edu:2445/163240 |
| Online Access: | https://hdl.handle.net/2445/163240 |
| Access Level: | Open access |
| Keyword: | Reaccions químiques Cicles biogeoquímics Chemical reactions Biogeochemical cycles |
| Summary: | Abstract: A convenient synthesis of an octacyclic compound containing an iodo and a trimethylsilyl group in vicinal double bridgehead positions, as a possible precursor of a pyramidalized alkene, is described. The key step of the synthesis consists of a double nucleophilic substitution of two neopentyl-type iodides by cyclopentadienide anions followed by two intramolecular Diels-Alder cycloadditions. All attempts to generate the expected pyramidalized alkene from the above precursor on reac-tion with different sources of fluoride failed. This octacyclic compound, which contains two disubstituted C=C bonds, underwent a chemo- and stereoselective Pd0-catalyzed co-cyclotrimerization with dimethyl acetylenedicarb-oxylate to give a nonacyclic cyclohexadiene derivative that can be aromatized upon reaction with CsF or transformed into a related fluoride upon reaction with AgF. |
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