Metal ion catalysis of phosphoryl hydrolysis from thiolphosphate monoesters

S. J. Benkovic, E. M. Miller

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The catalytic effect of metal ions on the hydrolysis of ethyl-S-phosphate (1a), cysteamine-S-phosphate (1b), and 2-carboxyethyl-S-phosphate (1c) has been investigated. Fe(III) and Al(III) markedly inhibit the rate of hydrolysis of all three thiolphosphates, decreasing kabs by ca. 102 at pH 3; Zn(II) and Mn(II) are almost without effect on the hydrolysis rates of 1b and 1c; and Cu(II) in less than substrate concentration increases kabs by 102 for 1b and 1c but has no effect on 1a. The requirement of a suitably located ligand for catalysis is obvious. The mechanism of the Cu(II)-catalyzed hydrolysis of 1b has been examined in detail and includes the following pertinent characteristics: (1) rate-determining formation of two hydrolytically labile complexes from monoanion (NH2RSPO3H-) and/or dianion (NH2RSPO32-) and Cu(H2O)12+; (2) product inhibition by cysteamine because of the formation of a catalytically inactive cysteamine-Cu(II) complex; and (3) incursion of an oxidative Cu(II)-catalyzed conversion of cysteamine to cystamine at pH 7, which relieves product inhibition. The synthetic phosphorylating potential of this reaction in acetonitrile-alcohol solvent mixtures indicates its utility in the synthesis of simple phosphate monoesters. A rationale for the effectiveness of Cu(II) catalysis in these systems is offered.

Original languageEnglish (US)
Pages (from-to)107-131
Number of pages25
JournalBioinorganic Chemistry
Volume1
Issue number2
DOIs
StatePublished - 1972

Fingerprint

Catalysis
Cysteamine
Metal ions
Hydrolysis
Metals
Ions
Phosphates
Cystamine
Alcohols
Ligands
Substrates

All Science Journal Classification (ASJC) codes

  • Biochemistry

Cite this

Benkovic, S. J. ; Miller, E. M. / Metal ion catalysis of phosphoryl hydrolysis from thiolphosphate monoesters. In: Bioinorganic Chemistry. 1972 ; Vol. 1, No. 2. pp. 107-131.
@article{fd6b5e3704b44e759bde3cf7c3d61af5,
title = "Metal ion catalysis of phosphoryl hydrolysis from thiolphosphate monoesters",
abstract = "The catalytic effect of metal ions on the hydrolysis of ethyl-S-phosphate (1a), cysteamine-S-phosphate (1b), and 2-carboxyethyl-S-phosphate (1c) has been investigated. Fe(III) and Al(III) markedly inhibit the rate of hydrolysis of all three thiolphosphates, decreasing kabs by ca. 102 at pH 3; Zn(II) and Mn(II) are almost without effect on the hydrolysis rates of 1b and 1c; and Cu(II) in less than substrate concentration increases kabs by 102 for 1b and 1c but has no effect on 1a. The requirement of a suitably located ligand for catalysis is obvious. The mechanism of the Cu(II)-catalyzed hydrolysis of 1b has been examined in detail and includes the following pertinent characteristics: (1) rate-determining formation of two hydrolytically labile complexes from monoanion (NH2RSPO3H-) and/or dianion (NH2RSPO32-) and Cu(H2O)12+; (2) product inhibition by cysteamine because of the formation of a catalytically inactive cysteamine-Cu(II) complex; and (3) incursion of an oxidative Cu(II)-catalyzed conversion of cysteamine to cystamine at pH 7, which relieves product inhibition. The synthetic phosphorylating potential of this reaction in acetonitrile-alcohol solvent mixtures indicates its utility in the synthesis of simple phosphate monoesters. A rationale for the effectiveness of Cu(II) catalysis in these systems is offered.",
author = "Benkovic, {S. J.} and Miller, {E. M.}",
year = "1972",
doi = "10.1016/S0006-3061(00)80118-0",
language = "English (US)",
volume = "1",
pages = "107--131",
journal = "Journal of Inorganic Biochemistry",
issn = "0162-0134",
publisher = "Elsevier Inc.",
number = "2",

}

Metal ion catalysis of phosphoryl hydrolysis from thiolphosphate monoesters. / Benkovic, S. J.; Miller, E. M.

In: Bioinorganic Chemistry, Vol. 1, No. 2, 1972, p. 107-131.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Metal ion catalysis of phosphoryl hydrolysis from thiolphosphate monoesters

AU - Benkovic, S. J.

AU - Miller, E. M.

PY - 1972

Y1 - 1972

N2 - The catalytic effect of metal ions on the hydrolysis of ethyl-S-phosphate (1a), cysteamine-S-phosphate (1b), and 2-carboxyethyl-S-phosphate (1c) has been investigated. Fe(III) and Al(III) markedly inhibit the rate of hydrolysis of all three thiolphosphates, decreasing kabs by ca. 102 at pH 3; Zn(II) and Mn(II) are almost without effect on the hydrolysis rates of 1b and 1c; and Cu(II) in less than substrate concentration increases kabs by 102 for 1b and 1c but has no effect on 1a. The requirement of a suitably located ligand for catalysis is obvious. The mechanism of the Cu(II)-catalyzed hydrolysis of 1b has been examined in detail and includes the following pertinent characteristics: (1) rate-determining formation of two hydrolytically labile complexes from monoanion (NH2RSPO3H-) and/or dianion (NH2RSPO32-) and Cu(H2O)12+; (2) product inhibition by cysteamine because of the formation of a catalytically inactive cysteamine-Cu(II) complex; and (3) incursion of an oxidative Cu(II)-catalyzed conversion of cysteamine to cystamine at pH 7, which relieves product inhibition. The synthetic phosphorylating potential of this reaction in acetonitrile-alcohol solvent mixtures indicates its utility in the synthesis of simple phosphate monoesters. A rationale for the effectiveness of Cu(II) catalysis in these systems is offered.

AB - The catalytic effect of metal ions on the hydrolysis of ethyl-S-phosphate (1a), cysteamine-S-phosphate (1b), and 2-carboxyethyl-S-phosphate (1c) has been investigated. Fe(III) and Al(III) markedly inhibit the rate of hydrolysis of all three thiolphosphates, decreasing kabs by ca. 102 at pH 3; Zn(II) and Mn(II) are almost without effect on the hydrolysis rates of 1b and 1c; and Cu(II) in less than substrate concentration increases kabs by 102 for 1b and 1c but has no effect on 1a. The requirement of a suitably located ligand for catalysis is obvious. The mechanism of the Cu(II)-catalyzed hydrolysis of 1b has been examined in detail and includes the following pertinent characteristics: (1) rate-determining formation of two hydrolytically labile complexes from monoanion (NH2RSPO3H-) and/or dianion (NH2RSPO32-) and Cu(H2O)12+; (2) product inhibition by cysteamine because of the formation of a catalytically inactive cysteamine-Cu(II) complex; and (3) incursion of an oxidative Cu(II)-catalyzed conversion of cysteamine to cystamine at pH 7, which relieves product inhibition. The synthetic phosphorylating potential of this reaction in acetonitrile-alcohol solvent mixtures indicates its utility in the synthesis of simple phosphate monoesters. A rationale for the effectiveness of Cu(II) catalysis in these systems is offered.

UR - http://www.scopus.com/inward/record.url?scp=0015471438&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0015471438&partnerID=8YFLogxK

U2 - 10.1016/S0006-3061(00)80118-0

DO - 10.1016/S0006-3061(00)80118-0

M3 - Article

AN - SCOPUS:0015471438

VL - 1

SP - 107

EP - 131

JO - Journal of Inorganic Biochemistry

JF - Journal of Inorganic Biochemistry

SN - 0162-0134

IS - 2

ER -