Hydrolysis of 8-Quinolyl Phosphate Monoester: Kinetic and Theoretical Studies of the Effect of Lanthanide Ions

被引：11

作者：

Souza, Bruno S. ^{[1
]}

Brandao, Tiago A. S. ^{[1
]}

Orth, Elisa S. ^{[1
]}

Roma, Ana C. ^{[2
]}

Longo, Ricardo L. ^{[2
]}

Bunton, Clifford A. ^{[3
]}

Nome, Faruk ^{[1
]}

机构：

[1] Univ Fed Santa Catarina, Dept Quim, BR-88040900 Florianopolis, SC, Brazil

[2] Univ Fed Recife, Dept Quim Fundamental, BR-50740540 Pernambuco, Brazil

[3] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2009年 / 74卷 / 03期

关键词：

MOLECULAR-ORBITAL METHODS; GAUSSIAN-TYPE BASIS; PHOSPHORYL TRANSFER; PROTEIN PHOSPHATASES; COMPLEXES; CATALYSIS; MECHANISM; DINUCLEAR; MODELS; EQUILIBRIA;

D O I：

10.1021/jo801870v

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

8-Quinolyl phosphate (8QP) in the presence of the trivalent lanthanide ions (Ln = La, Sm, Eu, Tb, and Er) forms a [Ln center dot 8QP](+) complex where the lanthanide ion catalyzes hydrolysis of 8QP. In reactions with Tb3+ or Er3+, there is evidence of limited intervention by a second lanthanide ion. Rate constants are increased by more than 10(7)-fold, and kinetic data and B3LYP/ECP calculations indicate that the effects are largely driven by leaving group and metaphosphate ion stabilization. The lanthanides favor a single-step D(N)A(N) mechanism with a dissociative transition state, with limited nucleophilic assistance, consistent with the low hydroxide ion dependence and the small kinetic effect of Ln(3+) radii.

引用

页码：1042 / 1053

页数：12

共 50 条

[11] Substituent effect on ESIPT and hydrogen bond mechanism of N-(8-Quinolyl) salicylaldimine: A detailed theoretical exploration
Ding, Sha
Xu, Aixiang
Sun, Aokui
Xia, Yong
Liu, Yuejun
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, 2021, 245
[12] Theoretical Modeling of the Reaction Mechanism of Phosphate Monoester Hydrolysis in Alkaline Phosphatase
Lopez-Canut, Violeta
Marti, Sergio
Bertran, Juan
Moliner, Vicente
Tunon, Inaki
JOURNAL OF PHYSICAL CHEMISTRY B, 2009, 113 (22): : 7816 - 7824
[13] STUDIES OF PHOSPHORYLATION .4. SELECTIVE PHOSPHORYLATION OF 5'-HYDROXY GROUP OF NUCLEOSIDES BY MEANS OF TIRS(8-QUINOLYL) PHOSPHATE
TAKAKU, H
SHIMADA, Y
TETRAHEDRON LETTERS, 1974, (14) : 1279 - 1282
[14] The effect of leaving group on mechanistic preference in phosphate monoester hydrolysis
Kamerlin, Shina C. L.
Wilkie, John
ORGANIC & BIOMOLECULAR CHEMISTRY, 2011, 9 (15) : 5394 - 5406
[15] STUDIES OF PHOSPHORYLATION .3. EFFECT OF METALLIC COMPOUND ON PHOSPHORYLATION OF ALCOHOLS, PHOSPHATES, AND NUCLEOSIDES BY 8-QUINOLYL PHOSPHATES
TAKAKU, H
SHIMADA, Y
CHEMICAL & PHARMACEUTICAL BULLETIN, 1974, 22 (08) : 1743 - 1747
[16] Resolving Apparent Conflicts between Theoretical and Experimental Models of Phosphate Monoester Hydrolysis
Duarte, Fernanda
Aqvist, Johan
Wiliams, Nicholas H.
Kamerlin, Shina C. L.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (03) : 1081 - 1093
[17] Theoretical evaluation of the substrate-assisted catalysis mechanism for the hydrolysis of phosphate monoester dianions
Iche-Tarrat, Nathalie
Ruiz-Lopez, Manuel
Barthelat, Jean-Claude
Vigroux, Alain
CHEMISTRY-A EUROPEAN JOURNAL, 2007, 13 (13) : 3617 - 3629
[18] Synthesis and structural studies of an (8-quinolyl)amido-lithium complex and its reaction with dimethylsilicone
Jones, C
Junk, PC
Smithies, NA
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2000, 607 (1-2) : 105 - 111
[19] ACID-CATALYZED AND METAL-ION-CATALYZED HYDROLYSIS OF 8-QUINOLYL BETA-D-GLUCOPYRANOSIDE
CLARK, CR
HAY, RW
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1973, (14): : 1943 - 1947
[20] PHOSPHORYLATION BY ACTIVE ESTER OF PHOSPHORIC-ACID .1. PREPARATION AND REACTION OF PHENYL 8-QUINOLYL PHOSPHATE
TAKAKU, H
SHIMADA, Y
CHEMICAL & PHARMACEUTICAL BULLETIN, 1973, 21 (02) : 445 - 447

← 1 2 3 4 5 →