Papers by Gaetano Tomaselli
Chemical Communications, 2014
A chiral organic-inorganic hybrid material, based on a porous silicon surface functionalized with... more A chiral organic-inorganic hybrid material, based on a porous silicon surface functionalized with a chiral cavitand, was designed and synthesized. The affinity of this device in water toward a bromine-marked alkyl-ammonium salt has been evaluated using XPS detection. UV and CD measurements highlight the enantioselective extraction from a racemic mixture in water of the S-enantiomer of the selected guest (ee ≥ 80%).
The Journal of Organic Chemistry, 1973
ABSTRACT
The Journal of Organic Chemistry, 1974
ABSTRACT
Cheminform, Feb 9, 1993
AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance th... more AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
European Journal of Organic Chemistry, Jul 1, 2010
A new heteroditopic chiral uranyl-salen complex incorporating two pyrenyl groups was designed and... more A new heteroditopic chiral uranyl-salen complex incorporating two pyrenyl groups was designed and synthesized for the recognition of ammonium salts, tetrabutylammonium (TBA) and tetramethylammonium (TMA) amino acids. UV/Vis measurements indicate the formation of 1:1 host-guest complexes with high association constants and an excellent en-
Journal of Molecular Catalysis a Chemical, Dec 1, 1996
Oxidation of N,N-benzylalkylamines in chloroform by Mo(VI) and W(VI) polyperoxo complexes (PPC) o... more Oxidation of N,N-benzylalkylamines in chloroform by Mo(VI) and W(VI) polyperoxo complexes (PPC) of general formula Q+3{PO4[MO(O2)2]4}3− (Q+ = onium ion) yield the corresponding nitrones as oxidized products quantitatively. Only in the case of N,N-benzylmethylamine the formation of nitrone is accompanied by 25% of benzaldoxime. Oxidation of N,N-benzyltertbutylamine and N,N-benzylisopropylamine follows second order kinetics. This finding does not disqualify the hypothesis that the reaction might occur by a rate determining nucleophilic attack of the amine onto the peroxide oxygens leading, through a Bartlett-type transition state, to the probable formation of the corresponding hydroxylamine, which then is converted to nitrone in a faster step. Under this respect PPC behavior seems related to that of the corresponding anionic monuclear oxidants Q+[MO(O2)2L]−) (L = anionic ligand). On the other hand PPC toward N,N-benzylmethylamine behave similar to neutral mononuclear oxidants, MO(O2)2L, since in both cases the formation of an oxidant-substrate association complex appears a probable event along the reaction coordinate. However, whereas for the neutral mononuclear oxidants this oxidant-substrate adduct seems to react further toward external amine molecules through a Bartlett-type transition state, for PPC such an adduct seems to evolve to products through unimolecular events akin enzymatic processes.
J Org Chem, 1992
Kinetics of oxidation of thioethers, alkenes, and sulfoxides by tetrahexylammonium tetrakis(diper... more Kinetics of oxidation of thioethers, alkenes, and sulfoxides by tetrahexylammonium tetrakis(diperoxo-mo1ybdo)phaephate (TEAM) were performed in chloroform. The results obtained, compared with the correaponding data of a series of Mo(V1) peroxo complexes, rule out a nucleophilic oxygen transfer mechanism. Rather, the data point to Mo(VI) peroxopolyoxo complexes as well as simple peroxo complexes behave as electrophilic oxidants toward nucleophilic substrates such as thioethers and alkenes. A study of the countercation effects indicates that the increasing bulkiness of the cation reduces the electrophilicity of the peroxopolyoxo complex. With sulfoxides, incursion of SET processes might be a likely event.
International Journal of Molecular Sciences, 2016
Chirality, 2015
The salen-type ligand prepared with (R,R) diphenylethan-1,2-diamine and salicylaldehyde provides ... more The salen-type ligand prepared with (R,R) diphenylethan-1,2-diamine and salicylaldehyde provides stable and inert complexes KLnL2 upon simple reaction with lanthanide halides or pseudohalides LnX3 (Ln = Tb(3+) -Lu(3+) ; X = Cl(-) or TfO(-) ) of its potassium salt. All the complexes were completely characterized through nuclear magnetic resonance (NMR), electronic circular dichroism (ECD) in the UV and some (Er(3+) , Tm(3+) , Yb(3+) ) also with Near-IR ECD (NIR-ECD) and luminescence (Tb(3+) , Tm(3+) ). Careful analysis of the NMR shifts demonstrated that the complexes are isostructural in solution and afforded an accurate geometry. This was further confirmed by means of Density Functional Theory (DFT) optimization of the Lu(3+) complex, and by comparing the ligand-centered experimental and time-dependent TD-DFT computed UV-ECD spectra. As final validation, we used the NIR-ECD spectrum of the Yb(3+) derivative calculated by means of Richardson's equations. The excellent match between calculated and experimental ECD spectra confirm the quality of the NMR structure. Chirality 00:000-000, 2015. © 2015 Wiley Periodicals, Inc.
New J. Chem., 2015
We designed and synthesized a new porphyrin-spermine derivative that self-assembles under hierarc... more We designed and synthesized a new porphyrin-spermine derivative that self-assembles under hierarchical control. Its aggregation processes depend on the protonation of both the spermine units and central core nitrogen atoms. Therefore, the time duration of pH titrations and/or the direct protonation of a specific site allow for choosing the desired aggregation state of the system. † Electronic supplementary information (ESI) available: All synthetic compounds were characterised by 1 H NMR, APT, 1D-zTOCSY, ESI-MS and UV-vis spectroscopy. See
Journal of the Chemical Society, Perkin Transactions 2, 1976
ABSTRACT
Tetrahedron Letters, 2015
Uploads
Papers by Gaetano Tomaselli