Synthetic models for the zinc sites in the methionine synthases

被引：86

作者：

Chiou, SJ ^{[1
]}

Innocent, J ^{[1
]}

Riordan, CG ^{[1
]}

Lam, KC ^{[1
]}

Liable-Sands, L ^{[1
]}

Rheingold, AL ^{[1
]}

机构：

[1] Univ Delaware, Dept Chem & Biochem, Newark, DE 19716 USA

来源：

INORGANIC CHEMISTRY | 2000年 / 39卷 / 19期

关键词：

D O I：

10.1021/ic000505q

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The syntheses and molecular structures of a series of tetrahedral zinc complexes designed to model the active sites in Escherichia coli methionine synthases are reported. [PhTt(tBu)]ZnBr (PhTt(tBu) = phenyltris((tert-butylthio)methyl)borate) was prepared and characterized crystallographically to provide entry into [S-3]ZnX complexes. Metathesis with KSPh yielded the phenylthiolato complex, [PhTt(tBU)]Zn(SPh), which represents a structural mimic of the homocysteine ligated form of the enzyme. Alternatively, [S2N]ZnX (X = Br, CH3, SPh) species were prepared using the new mixed-donor ligands, [Ph(pz)Bt(tBu)] (phenyl(pyrazolyl)bis((tert-butylthio)met and [Ph(pz(tBu))Bt(tBu)] (phenyl(3-tert-butylpyrazolyl)bis((tert-butylthio. Protonolysis of [Ph(pz(tBu))Bt(tBu)]Zn(CH3) by PhSH in toluene yielded [Ph(pz(tBu))Bt(tBu)] Zn(SPh), a synthetic analogue of the homocysteine ligated form of cobalamin-independent methionine synthase (Met E). The average Zn-S bond distance in [Ph(pz(tBu))Bt(tBu)]Zn(SPh) of 2.37 Angstrom compares well with the EXAFS-derived distance of 2.31 Angstrom found in the homocysteine-bound form of Met E.

引用

页码：4347 / 4353

页数：7

共 31 条

[1] A role for coenzyme M (2-mercaptoethanesulfonic acid) in a bacterial pathway of aliphatic epoxide carboxylation [J].

Allen, JR ;

Clark, DD ;

Krum, JG ;

Ensign, SA .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1999, 96 (15) :8432-8437

[2] The refined crystal structure of Drosophila lebanonensis alcohol dehydrogenase at 1.9 Å resolution [J].

Benach, J ;

Atrian, S ;

Gonzàlez-Duarte, R ;

Ladenstein, R .

JOURNAL OF MOLECULAR BIOLOGY, 1998, 282 (02) :383-399

[3] Protonation of the hydroxide ligand in a synthetic analogue of carbonic anhydrase, [TpBut,Me]ZnOH:: inhibition of reactivity towards CO2 [J].

Bergquist, C ;

Parkin, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (26) :6322-6323

[4] STRUCTURE OF ASTACIN AND IMPLICATIONS FOR ACTIVATION OF ASTACINS AND ZINC-LIGATION OF COLLAGENASES [J].

BODE, W ;

GOMISRUTH, FX ;

HUBER, R ;

ZWILLING, R ;

STOCKER, W .

NATURE, 1992, 358 (6382) :164-167

[5] A NEW TRIDENTATE N,N,S LIGAND AND ITS ZINC-COMPLEXES [J].

BRAND, U ;

VAHRENKAMP, H .

INORGANIC CHEMISTRY, 1995, 34 (12) :3285-3293

[6] Recombinant human liver betaine-homocysteine S-methyltransferase:: Identification of three cysteine residues critical for zinc binding [J].

Breksa, AP ;

Garrow, TA .

BIOCHEMISTRY, 1999, 38 (42) :13991-13998

[7] Pyrazolyl[(methylthio)methyl]borates: hybrid ligands providing nitrogen and sulfur donors [J].

Chiou, SJ ;

Ge, PH ;

Riordan, CG ;

Liable-Sands, LM ;

Rheingold, AL .

CHEMICAL COMMUNICATIONS, 1999, (02) :159-160

[8] Crystal structure of methyl coenzyme M reductase: The key enzyme of biological methane formation [J].

Ermler, U ;

Grabarse, W ;

Shima, S ;

Goubeaud, M ;

Thauer, RK .

SCIENCE, 1997, 278 (5342) :1457-1462

[9] POLY(METHYLTHIOMETHYL)BORATES - A NEW CLASS OF SULFUR-RICH LIGANDS FOR METAL-IONS [J].

GE, PH ;

HAGGERTY, BS ;

RHEINGOLD, AL ;

RIORDAN, CG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (18) :8406-8407

[10] Modeling the active sites of bacteriophage T7 lysozyme, bovine 5-aminolevulinate dehydratase, and peptide deformylase:: synthesis and structural characterization of a bis(pyrazolyl)(thioalkoxy)hydroborato zinc complex, [(Ph2CHS)BpBu-t,Pr-i]ZnI [J].

Ghosh, P ;

Parkin, G .

CHEMICAL COMMUNICATIONS, 1998, (03) :413-414

← 1 2 3 4 →