caa a22 4500 469060018 CHVBK 20180323132854.0 cr unu---uuuuu 170328e19920901xx s 000 0 eng 10.1007/BF01045981 doi (NATIONALLICENCE)springer-10.1007/BF01045981 A new ligand-functionalized β -cyclodextrin as a esterolytic reagent at neutral pH [Elektronische Daten] [Roberto Fornasier, Ennio Scarpa, Paolo Scrimin, Paolo Tecilla, Umberto Tonellato] The paper reports the synthesis of aβ-cyclodextrin (β-CD) derivative (1) functionalized with a ligand subunit at the secondary-hydroxyl rim. The ligand subunit is 2-hydroxymethyl-6-thiomethyl pyridine connected to the macrocycle via a thioether bond. In the presence of Cu(II) ions1 accelerates the cleavage of thep-nitrophenyl esters of picolinic acid (PNPP), quinaldic acid (PNPQ) and its 6-phenyl derivative (PNPQPh) via the nucleophilic attack of the hydroxyl of the pyridine subunit. However, theβ-CD derivative is less effective than the ligand 2-hydroxymethyl-6-methylthiomethyl pyridine (2), indicating no cooperation between the hydrophobic and metal ion recognition sites. However, in the case of PNPQPh, the observed rate constants in the presence of Cu(II) ions are close to that of model2 and this suggests we are approaching a binding mode appropriate for taking advantage of the two binding sites of the metal receptor1 · Cu(II). Interestingly, the most reactive derivative with nativeβ-CD is thep-nitrophenyl quinaldate (PNPQ) in accord with its mode of complexation to the macrocycle and the location of the actual nucleophile (one of the secondary hydroxyls ofβ-CD). Kluwer Academic Publishers, 1992 Cyclodextrin nationallicence transacylation nationallicence metal nationallicence Cu(II) nationallicence catalysis nationallicence ester nationallicence supramolecule nationallicence Fornasier Roberto Department of Organic Chemistry and Centro CNR Meccanismi Reazioni Organiche, Universita' di Padova, Via Marzolo 1, 35131, Padova, Italy aut Scarpa Ennio Department of Organic Chemistry and Centro CNR Meccanismi Reazioni Organiche, Universita' di Padova, Via Marzolo 1, 35131, Padova, Italy aut Scrimin Paolo Department of Organic Chemistry and Centro CNR Meccanismi Reazioni Organiche, Universita' di Padova, Via Marzolo 1, 35131, Padova, Italy aut Tecilla Paolo Department of Organic Chemistry and Centro CNR Meccanismi Reazioni Organiche, Universita' di Padova, Via Marzolo 1, 35131, Padova, Italy aut Tonellato Umberto Department of Organic Chemistry and Centro CNR Meccanismi Reazioni Organiche, Universita' di Padova, Via Marzolo 1, 35131, Padova, Italy aut Journal of inclusion phenomena and molecular recognition in chemistry Kluwer Academic Publishers 14/3-4(1992-09-01), 205-215 0923-0750 14:3-4<205 1992 14 10847 https://doi.org/10.1007/BF01045981 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF01045981 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Fornasier Roberto Department of Organic Chemistry and Centro CNR Meccanismi Reazioni Organiche, Universita' di Padova, Via Marzolo 1, 35131, Padova, Italy aut NATIONALLICENCE 700 1- Scarpa Ennio Department of Organic Chemistry and Centro CNR Meccanismi Reazioni Organiche, Universita' di Padova, Via Marzolo 1, 35131, Padova, Italy aut NATIONALLICENCE 700 1- Scrimin Paolo Department of Organic Chemistry and Centro CNR Meccanismi Reazioni Organiche, Universita' di Padova, Via Marzolo 1, 35131, Padova, Italy aut NATIONALLICENCE 700 1- Tecilla Paolo Department of Organic Chemistry and Centro CNR Meccanismi Reazioni Organiche, Universita' di Padova, Via Marzolo 1, 35131, Padova, Italy aut NATIONALLICENCE 700 1- Tonellato Umberto Department of Organic Chemistry and Centro CNR Meccanismi Reazioni Organiche, Universita' di Padova, Via Marzolo 1, 35131, Padova, Italy aut NATIONALLICENCE 773 0- Journal of inclusion phenomena and molecular recognition in chemistry Kluwer Academic Publishers 14/3-4(1992-09-01), 205-215 0923-0750 14:3-4<205 1992 14 10847 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer