Straightforward synthesis of a vicinal double bridgehead iodo trimethylsilyl octacycle: unprecedented lack of reactivity of the silyl group in front of fluoride anions.

Camps García, PelayoLozano Mena, DavidGuitián, E.Peña, D.Pérez, D.Font Bardia, Ma. MercedesLlamas-Saíz, A.L.2020-05-302020-05-302017-03-271434-193Xhttps://hdl.handle.net/2445/163240Abstract: 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.33 p.application/pdfeng(c) Wiley-VCH, 2017Reaccions químiquesCicles biogeoquímicsChemical reactionsBiogeochemical cyclesStraightforward synthesis of a vicinal double bridgehead iodo trimethylsilyl octacycle: unprecedented lack of reactivity of the silyl group in front of fluoride anions.info:eu-repo/semantics/article6669532020-05-30info:eu-repo/semantics/openAccess