Search results for "Carbocation"
showing 7 items of 17 documents
Monoradicals and Diradicals of Dibenzofluoreno[3,2-b]fluorene Isomers: Mechanisms of Electronic Delocalization
2020
The preparation of a series of dibenzo- and tetrabenzo-fused fluoreno[3,2-b]fluorenes is disclosed, and the diradicaloid properties of these molecules are compared with those of a similar, previously reported series of anthracene-based diradicaloids. Insights on the diradical mode of delocalization tuning by constitutional isomerism of the external naphthalenes has been explored by means of the physical approach (dissection of the electronic properties in terms of electronic repulsion and transfer integral) of diradicals. This study has also been extended to the redox species of the two series of compounds and found that the radical cations have the same stabilization mode by delocalization…
Configuration of Enolates of β-Ketocarboxylic Acid Esters — Carbocation-Carbanion Salts
1996
Deprotonation of (Z)- or (E)-3-hydroxy-2,3-dimesitylpropenoic acid methyl ester (1a) with tetrakis(dimethylamino)-methane (3) led to stable salt (E)-2a, which belongs to a very rare species of salts that consist of a heteroatom-stabilized carbocation and a heteroatom-stabilized carbanion. An analogous guanidinium salt (E)-2b was formed in the reaction of 3-oxo-2,3-diphenylpropanoic acid methyl ester (1b) and 3. The molecular structures of these enolates were studied by NMR spectroscopy and an X-ray analysis of (E)-2a {MC[N(CH3)2]3} and compared with those of the corresponding alkali enolates.
Aryl carbinols as nerve agent probes. Influence of the conjugation on the sensing properties
2012
Two new aryl carbinols (1 and 3) have been synthesised and characterised and their ability as OFF-ON probes for the chromogenic detection of the nerve agent simulant in acetonitrile has been tested. In addition compound 2 has been also studied. The carbinols suffered a phosphorylation reaction followed by an elimination process giving rise to the corresponding carbocations. This transformation of the carbinol into the carbocation is responsible for a significant color change. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012.
Rearrangement of 4,5-epoxy-9-trimethylsilyldecalines. Application to the synthesis of the natural eremophilane (-)-aristolochene.
2006
Several 4,5-epoxy-9-trimethylsilyl-eudesmanes and 15-nor-eudesmanes, having different relative stereochemistry and substitution at the oxirane ring, have been prepared starting from (-)-carvone and subjected to acid-promoted rearrangement. The presence of the silicon at C9 favors two different main reaction pathways involving C14-methyl or C1-methylene migration through the stabilization of a C10 carbocation intermediate. Selective 1,2-migration of the bridgehead methyl group takes place with trisubstituted beta-epoxide and tetrasubstituted alpha-epoxide, yielding 4-hydroxy-eremophilane and 15-nor-eremophilane compounds, while the trisubstituted alpha-epoxide suffers successive rearrangemen…
Tris(2-thienyl)methyl cation; An unprecedent 13C NMR behavior
1986
Abstract An unexpected response of the chemical shift value to the substitution of phenyl by thienyl groups is found in the series 1–8 . On this basis the planar cation 7 appears to show an homoaromatic-like peripheral ring current.
Synthesis of Sesquiterpenes via silicon-guided rearrangement of epoxydecalins
2008
A survey of the rearrangement of methyldecalins via C-5 carbocation intermediates, with special attention to the silicon-guided rearrangement of epoxydecalins is provided. A TMS group properly positioned on either C-1 or C-9 promotes the acidic rearrangement of 10-methyl-4,5-epoxydecalins and 10-methyl-5,6-epoxydecalins with exclusive migration toward C-5 of the methyl or methylene groups linked directly to C-10. The application of this biomimetic approach to the synthesis of a number of spirocyclic and eremophilane sesquiterpenes is reported.
Water compatible gold(III)-catalysed synthesis of unsymmetrical ethers from alcohols.
2008
An efficient and broad-scoped method for the preparation of unsymmetrical ethers from alcohols catalysed by the simplest and least expensive gold catalyst, NaAuCl 4 , is described for the first time. The procedure enables the etherification of benzylic and tertiary alcohols with moderate to good yields under mild conditions with low catalyst loading. Symmetrical ethers, the usual side products in the etherification of alcohols, were not detected in this case. The formation of the racemic ether from a chiral benzyl alcohol suggests the intermediacy of a carbocation, which has not previously been postulated for gold-catalysed reactions involving alcohols.