Polyhydroxylated Sapphyrins:  Multisite Non-metallic Catalysts for Activated Phosphodiester Hydrolysis

• Published in: Journal of the American Chemical Society Vol. 128; no. 2; pp. 432 - 437
• Main Authors: Král, Vladimír, Lang, Kamil, Králová, Jarmila, Dvořák, Michal, Martásek, Pavel, Chin, Aileen O, Andrievsky, Andrei, Lynch, Vincent, Sessler, Jonathan L
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 18.01.2006; Amer Chemical Soc
• Subjects: Catalysis; Chemistry; Chemistry, Multidisciplinary; Exact sciences and technology; Hydrogen Bonding; Hydrolysis; Hydroxylation; Kinetics; Kinetics and mechanisms; Molecular Structure; Nitrophenols - chemistry; Organic chemistry; Physical Sciences; Porphyrins - chemistry; Reactivity and mechanisms; Science & Technology; X-Ray Diffraction; GUANIDINIUM GROUPS; COMPLEX; PHOSPHORYL-TRANSFER-REACTIONS; MECHANISM; DINUCLEAR; COOPERATIVITY; METAL-IONS; RECEPTORS; PHOSPHATE DIESTERS; ANION-BINDING; Catalytic reaction; Nitrogen heterocycle; Experimental study; Buffer solution; Phosphorus Organic compounds; Macrocycle; Hydrolysis; Homogeneous catalysis; Reaction mechanism; Organic phosphate; Kinetic parameter; Rate constant; Catalyst activity
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja0518474

Enhanced hydrolysis rates for the cleavage of bis(4-nitrophenyl)phosphate (BNPP), a model phosphodiester, may be achieved by using appropriately designed ditopic receptors containing the known phosphate-binding nucleus, sapphyrin, attached covalently to suitably oriented polyhydroxyl subunits. Evidence for the interaction between sapphyrin and BNPP comes from solid-state X-ray diffraction analysis of a diprotonated dihydroxylated sapphyrin−BNPP complex and from solution-phase 31P NMR spectroscopic binding studies. The sapphyrins described in this paper may have a role to play as oligonucleotide cleavage agents.