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91.
92.
Valentina Bleve Christian Schäfer Dr. Paola Franchi Dr. Serena Silvi Prof. Dr. Elisabetta Mezzina Prof. Dr. Alberto Credi Prof. Marco Lucarini 《ChemistryOpen》2015,4(1):2-21
An acid–base switchable molecular shuttle based on a [2]rotaxane, incorporating stable radical units in both the ring and dumbbell components, is reported. The [2]rotaxane comprises a dibenzo[24]crown-8 ring (DB24C8) interlocked with a dumbbell component that possesses a dialkylammonium (NH2+) and a 4,4′-bipyridinium (BPY2+) recognition site. Deprotonation of the rotaxane NH2+ centers effects a quantitative displacement of the DB24C8 macroring to the BPY2+ recognition site, a process that can be reversed by acid treatment. Interaction between stable 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radicals connected to the ring and dumbbell components could be switched between noncoupled (three-line electron paramagnetic resonance (EPR) spectrum) and coupled (five-line EPR spectrum) upon displacement of the spin-labelled DB24C8 macroring. The complete base- and acid-induced switching cycle of the EPR pattern was repeated six times without an appreciable loss of signal, highlighting the reversibility of the process. Hence, this molecular machine is capable of switching on/off magnetic interactions by chemically driven reversible mechanical effects. A system of this kind represents an initial step towards a new generation of nanoscale magnetic switches that may be of interest for a variety of applications. 相似文献
93.
Graziano Baccolini Giorgio Orsolan Elisabetta Mezzina Paolo Sgarabotto Corrado Rizzoli 《Heteroatom Chemistry》1994,5(1):37-42
Fused 1,3-benzothiaphospholes 2 (cis-2,6,10-trimethyl-[1, 3]benzothiaphospholo[2,3-b][1, 3]benzothiaphosphole) reacts with H2O2 and S8, giving the corresponding oxide and sulfide, respectively. The reactions of 2 with diethyl azodicarboxylate (DEAD)/catechol or DEAD/o-aminophenol, o-azidophenol, and tetrachloro-o-benzoquinone (TOB) give the first examples of spiro pentacoordinated phosphorus derivatives of this heterocyclic system. The X-ray structural analysis of spiro compound 3 showed a trigonal bipyramidal configuration at phosphorus in which the three rings assume axial-equatorial positions. 相似文献
94.
Benincori T Brenna E Sannicolò F Trimarco L Antognazza P Cesarotti E Demartin F Pilati T 《The Journal of organic chemistry》1996,61(18):6244-6251
The synthesis and application of three examples of a new class of chiral (C(2)) atropisomeric diphosphines characterized by two interconnected five-membered heteroaromatic rings, with hindered rotation around the interanular bond, are described. Optically pure (+)- and (-)-2,2'-bis(diphenylphosphino)-4,4',6,6'-tetramethyl-3,3'-bibenzo[b]thiophene (tetraMe-bitianp) (1a) and the parent unsubstituted system (+)- and (-)-bitianp (1b) were synthesized. They were found to be optically stable at 100 degrees C and were successfully employed as ligands in the Ru(II)-catalyzed hydrogenation of alpha- and beta-oxo esters to the corresponding alpha- and beta-hydroxy esters and in the hydrogenation of olefinic substrates. The optical and chemical yields were comparable with those reported for the same Ru(II)-binap-catalyzed reactions carried out under the same experimental conditions. The 2,2'-bis(diphenylphosphino)-3,3'-bibenzo[b]furan (1c), the oxygenated analogue of bitianp, was found to be configurationally unstable at room temperature. Complete structural X-ray elucidation of the Pd complexes of 1a-c is reported. The advantages of these biheteroaromatic ligands over the classical biaryl systems are discussed. 相似文献
95.
96.
Elisabetta Ranucci Gloria Spagnoli Paolo Ferruti 《Macromolecular rapid communications》1999,20(1):1-6
A novel activated derivative of methacrylic acid, namely 2‐[(1‐imidazolyl)formyloxy]ethyl methacrylate was synthesized and homopolymerized. The resulting polymer was used in exchange reactions with alcohols and amines, thus showing a potential for the synthesis of multifunctional polymers. All reactions, expecially those carried out in the presence of amines, proceeded under mild conditions. 2‐[(1‐Imidazolyl)formyloxy]ethyl methacrylate can also be regarded as a valuable precursor for the preparation of new and easily polymerizable functional monomers. 相似文献
97.
Elisabetta Brenna Claudio Fuganti Giovanni Fronza Luciana Malpezzi Annalisa Righetti Stefano Serra 《Helvetica chimica acta》1999,82(12):2246-2259
The preparation of (−)- and (+)-trans-α-irone ( 1a and 1b , resp.) and of (+)- and (−)-cis-α-irone ( 1c and 1d , resp.) from commercially available Irone alpha ® is reported. The relevant step in the synthetic sequence is the initial chromatographic separation of crystalline (±)-4,5-epoxy-4,5-dihydro-cis-α-irone ((±)- 5 ) from oily (±)-4,5-epoxy-4,5-dihydro-trans-α-irone ((±)- 4 ). The latter was subsequently converted, after NaBH4 reduction, into the crystalline 3,5-dinitrobenzoate ester (±)- 8 , thus allowing a complete separation of the two corresponding diastereoisomeric alcohol derivatives. Suitable enantiomerically pure precursors of the desired products 1a – d were obtained by kinetic resolution of the racemic allylic alcohols derived from (±)- 5 and (±)- 8 , mediated by lipase PS (Amano). The last steps consisted of MnO2 oxidation and removal of the epoxy moiety with Me3SiCl/NaI in MeCN. External panel olfactory evaluation showed that (−)-cis-α-irone ( 1d ) has the finest and most distinct `orris butter' character. 相似文献
98.
99.
Fruh D Chiarparin E Pelupessy P Bodenhausen G 《Journal of the American Chemical Society》2002,124(15):4050-4057
A method is described to determine long-range cross-correlations between the modulations of an anisotropic chemical shift (e.g., of a C' carbonyl carbon in a protein) and the fluctuations of a weak long-range dipolar interaction (e.g., in cross-correlation between the same C' carbonyl and the H(N) proton of the neighboring amide group). Such long-range correlations are difficult to measure because the corresponding long-range scalar couplings are so small that Redfield's secular approximation is often violated. The method, which combines features of single- and double-quantum NMR spectroscopy, allows one to cancel the effects of dominant short-range dipolar interactions (e.g., between the CSA of the amide nitrogen N and the dipolar coupling to its attached proton H(N)) and is designed so that the secular approximation is rescued even if the scalar coupling between the long-range dipolar coupling partners is very small. The cross-correlation rates thus determined in ubiquitin cover a wide range because of local motions and variations of the CSA tensors. 相似文献
100.
Arduini A Brindani E Giorgi G Pochini A Secchi A 《The Journal of organic chemistry》2002,67(17):6188-6194
A novel heteroditopic receptor (5) based on a rigid calix[4]arene cavity bearing at the upper rim four arylsulfonamido binding sites has been synthesized. The binding abilities of this new host have been investigated in apolar solvents toward a series of tetramethylammonium salts (tosylate, chloride, acetate, trifluoroacetate, and picrate) and compared with those of monotopic and heteroditopic calix[4]arene-bis(crown-3)-based receptors 1 and 2 in order to evaluate the role of the anion on ion-pair recognition. While monotopic host 1 shows an efficiency order toward the different salts that increases when the anion is less interactive (Hofmeister trend), an opposite role of the counteranion on the recognition process was observed with host 5 (anti-Hofmeister trend). A more complex behavior is experienced by host 2, which shows a high and leveled efficiency for all the anions tested. The results obtained were explained on the basis of the different types of ion pairs present in the recognition process. Further information on the role of the anion were obtained by the "dual host" strategy utilizing the tri-n-butylthioureido derivative of tren 7, which forms a stable complex with chloride anion. The very high efficiency shown by these heteroditopic hosts opens new routes in supramolecular projects and is a very interesting tool in the molecular recognition of ion-pairs and its applications. 相似文献