The second isolable B12-thiolate complex, (pentafluorophenylthiolato)cobalamin:: Synthesis and characterization

被引：20

作者：

Hsu, TLC ^{[1
]}

Brasch, NE ^{[1
]}

Finke, RG ^{[1
]}

机构：

[1] Colorado State Univ, Dept Chem, Ft Collins, CO 80523 USA

来源：

INORGANIC CHEMISTRY | 1998年 / 37卷 / 20期

关键词：

D O I：

10.1021/ic9704750

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The synthesis, isolation, and characterization of (pentafluorophenylthiolato)cobalamin, C(6)F(5)SCbl, are reported, only the second isolable RSCbl known. The synthesis of C(6)F(5)SCbl in 81% yield is accomplished by the dropwise addition of 0.93 equiv of C6F5SH in MeOH under argon to 1 equiv of HOCbl . HOAc (50.7 mg) in MeOH, all at -15 degrees C and under darkened, red-light-only conditions. The desired C6F5SCbl product was precipitated by the addition of cold, degassed acetone, isolated, and then characterized by FABMS and UV-visible, H-1 NMR, and F-19 NMR spectroscopies. Also reported is a H-1 NMR method for the detection of impurities in cobalamins. With the requisite, isolable RSCbl precursor to RS. and (.)Cbl radicals now in hand, the needed chemical precedent studies of the proposed H-. abstraction step from the substrate in ribonucleoside triphosphate reductase by a RS. analogue of the protein-S-. site an now possible.

引用

页码：5109 / 5116

页数：8

共 113 条

[41] Electron paramagnetic resonance investigations of a kinetically competent intermediate formed in ribonucleotide reduction: Evidence for a thiyl radical-Cob(II)alamin interaction [J].

Gerfen, GJ ;

Licht, S ;

Willems, JP ;

Hoffman, BM ;

Stubbe, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (35) :8192-8197

[42]

Giannotti C, 1982, B12, V1, P393

[43]

HAMA MSA, 1994, J CHEM SOC DA, P1367

[44]

HANANIA GIH, 1964, J CHEM SOC, VS, P5694

[45] THERMOLYSIS OF THE CO-C BOND IN ADENOSYLCORRINS .3. QUANTIFICATION OF THE AXIAL BASE EFFECT IN ADENOSYLCOBALAMIN BY THE SYNTHESIS AND THERMOLYSIS OF AXIAL BASE-FREE ADENOSYLCOBINAMIDE - INSIGHTS INTO THE ENERGETICS OF ENZYME-ASSISTED COBALT CARBON BOND HOMOLYSIS [J].

HAY, BP ;

FINKE, RG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (26) :8012-8018

[46] THERMOLYSIS OF THE CO-C BOND IN ADENOSYLCOBALAMIN (COENZYME B-12) .4. PRODUCTS, KINETICS AND CO-C BOND-DISSOCIATION ENERGY STUDIES IN ETHYLENE-GLYCOL [J].

HAY, BP ;

FINKE, RG .

POLYHEDRON, 1988, 7 (16-17) :1469-1481

[47] THERMOLYSIS OF THE CO-C BOND OF ADENOSYLCOBALAMIN .2. PRODUCTS, KINETICS, AND CO-C BOND-DISSOCIATION ENERGY IN AQUEOUS-SOLUTION [J].

HAY, BP ;

FINKE, RG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (16) :4820-4829

[48] PHOTOCHEMISTRY OF AZIDO AND THIOLATO VITAMIN-B12 MODEL COMPLEXES AS PRECURSOR COMPOUNDS FOR COORDINATIVELY UNSATURATED COBALT(II) COMPLEXES [J].

HENNIG, H ;

RITTER, K .

JOURNAL FUR PRAKTISCHE CHEMIE-CHEMIKER-ZEITUNG, 1995, 337 (02) :125-132

[49]

HILL HAO, 1969, CHEM BRIT, V5, P156

[50] CHEMISTRY OF VITAMIN-B12 - CO-ORDINATION OF BIOLOGICALLY IMPORTANT MOLECULES [J].

HILL, HAO ;

PRATT, JM ;

THORP, RG ;

WARD, B ;

WILLIAMS, RJP .

BIOCHEMICAL JOURNAL, 1970, 120 (02) :263-+

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