The calix[4]arene scaffold, blocked in the cone conformation by proper alkylation of the lower rim hydroxyls, was used as a convenient molecular platform for the design of bi- and trimetallic Zn2+ catalysts. The catalytic activity of the Zn2+ complexes of calix[4]arenes decorated at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with 2,6-bis[(dimethylamino)methyl]pyridine units were investigated in the cleavage of ester 6 and of the RNA model compound HPNP. High rate enhancements, up to 4 orders of magnitude, were observed in a number of catalyst-substrate combinations. Interestingly the order of catalytic efficiency among regioisomeric dinuclear complexes in the cleavage of ester 6 is 1,2-vicinal much greater than 1,3-distal, but it is reversed in the reaction of HPNP. The higher efficiency of trinuclear compared to dinuclear complexes provides an indication of the cooperation of three Zn2+ ions in the catalytic mechanism.

Cacciapaglia, R., Casnati, A., Mandolini, L., Reinhoudt, D.n., Salvio, R., Sartori, A., et al. (2005). Di- and trinuclear Zn2+ complexes of calix[4]arene based ligands as catalysts of acyl and phosphoryl transfer reactions. JOURNAL OF ORGANIC CHEMISTRY, 70(2), 624-630 [10.1021/jo0487350].

Di- and trinuclear Zn2+ complexes of calix[4]arene based ligands as catalysts of acyl and phosphoryl transfer reactions

Salvio R.;
2005-01-01

Abstract

The calix[4]arene scaffold, blocked in the cone conformation by proper alkylation of the lower rim hydroxyls, was used as a convenient molecular platform for the design of bi- and trimetallic Zn2+ catalysts. The catalytic activity of the Zn2+ complexes of calix[4]arenes decorated at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with 2,6-bis[(dimethylamino)methyl]pyridine units were investigated in the cleavage of ester 6 and of the RNA model compound HPNP. High rate enhancements, up to 4 orders of magnitude, were observed in a number of catalyst-substrate combinations. Interestingly the order of catalytic efficiency among regioisomeric dinuclear complexes in the cleavage of ester 6 is 1,2-vicinal much greater than 1,3-distal, but it is reversed in the reaction of HPNP. The higher efficiency of trinuclear compared to dinuclear complexes provides an indication of the cooperation of three Zn2+ ions in the catalytic mechanism.
2005
Pubblicato
Rilevanza internazionale
Articolo
Esperti anonimi
Settore CHIM/06 - CHIMICA ORGANICA
English
Con Impact Factor ISI
Cacciapaglia, R., Casnati, A., Mandolini, L., Reinhoudt, D.n., Salvio, R., Sartori, A., et al. (2005). Di- and trinuclear Zn2+ complexes of calix[4]arene based ligands as catalysts of acyl and phosphoryl transfer reactions. JOURNAL OF ORGANIC CHEMISTRY, 70(2), 624-630 [10.1021/jo0487350].
Cacciapaglia, R; Casnati, A; Mandolini, L; Reinhoudt, Dn; Salvio, R; Sartori, A; Ungaro, R
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/247935
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