Mixed sugar-core-phosphate chelation of d-fructose 1,6-bisphosphate with the ReVO(tmen) metal fragment

Article abstract of DOI:10.1039/c3dt32901a

Sugar phosphates provide metal-binding sites both at their sugar core and at their phosphate group(s). Mixed sugar-core-phosphate chelation has been considered as a typical bonding mode within the physiological pH range for the central metabolite d-fructose 1,6-bisphosphate. The Re^VO(tmen) metal fragment was used to enrich this coordination type. The formation of the [ReO(tmen)(Fruf2,3H_-21,6P₂H₂- κ³O^2,3,P1)]^- monoanion was determined by NMR spectroscopy and mass spectrometry. The model compound rac-glycerol 1-phosphate yielded similar results in terms of NMR spectroscopy. Crystal-structure analyses of [ReO(tmen)(rac-Glyc2,3H_-21PH- κ³O^2,3,P)]·2H₂O and [ReO(phen)(rac-Glyc2,3H_-21PH-κ³O^2,3,P)] ·MeOH confirmed the coordination pattern.

Full text of DOI:10.1039/c3dt32901a

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Mixed sugar-core–phosphate chelation of D-fructose
V
1
,6-bisphosphate with the Re O(tmen) metal
Cite this: Dalton Trans., 2013, 42, 5749
fragment†
Martin Steinborn, Mihael Suhanji and Peter Klüfers*
Sugar phosphates provide metal-binding sites both at their sugar core and at their phosphate group(s).
Mixed sugar-core–phosphate chelation has been considered as a typical bonding mode within the physio-
V
logical pH range for the central metabolite D-fructose 1,6-bisphosphate. The Re O(tmen) metal frag-
ment was used to enrich this coordination type. The formation of the [ReO(tmen)(Fruf2,3H−21,6-
Received 4th December 2012,
Accepted 12th February 2013
-κ O2,3,P1)]− monoanion was determined by NMR spectroscopy and mass spectrometry. The model
3
P
2
H
2
compound rac-glycerol 1-phosphate yielded similar results in terms of NMR spectroscopy. Crystal-structure
DOI: 10.1039/c3dt32901a
3
2,3,P
3
2,3,P
analyses of [ReO(tmen)(rac-Glyc2,3H−21PH-κ O
)]·2H
2
O and [ReO(phen)(rac-Glyc2,3H−21PH-κ O
)]·
www.rsc.org/dalton
MeOH confirmed the coordination pattern.
Introduction
Sugar phosphates play an important role in all organisms.
They are ubiquitous in metabolic pathways such as the
pentose phosphate pathway or glycolysis. Some reactions of
these pathways are catalysed by metalloenzymes that contain
1
,2
3
4–8
divalent metal centres, namely magnesium, iron or zinc,
in their active sites. The dications are assumed to become che-
lated by the sugar–phosphate substrates during the catalysed
reaction. Examples for such metalloenzymes include class-II
4
,5
1,2
aldolase,
ribulose 1,5-bisphosphate carboxylase
and
6
glucose 6-phosphate isomerase. Crystal-structure analyses of
enzymes loaded with their natural substrates are available for
all these examples and show the sugar phosphate in its acti-
vated form. However, information on the rules of metal chela-
tion by sugar phosphates in their stable state is sparse.
Depending on the pH value, various sugar phosphate
bonding modes appear to be accessible. In the extreme cases
of alkaline and acidic solutions, either the deprotonated
hydroxy functions of the sugar core chelate the metal or only
9
,10
the phosphate groups coordinate, respectively.
Mixed
sugar-core–phosphate chelation as a typical bonding mode
close to the physiological pH has been considered particularly
for the significant bioligand D-fructose 1,6-bisphosphate.
Thus, Scheme 1 shows the mixed bonding mode as deduced
Scheme 1 Mixed sugar-core–phosphate ligation of D-fructose 1,6-bisphos-
II
III
phate in the presence of the metal fragments Pd (en) and Al (tacn) as con-
cluded from NMR-spectroscopic experiments.
II
from NMR spectra for the metal fragments Pd (en) and
III
Al (tacn) (en
= ethane-1,2-diamine, tacn = 1,4,7-triaza-
9
cyclononane).
Department Chemie der Ludwig-Maximilians-Universität, Butenandtstr. 5-13, 81377
Munich, Germany. E-mail: kluef@cup.uni-muenchen.de
In fact, this coordination pattern was found in the enzyme
,4-dihydroxy-2-butanone-4-phosphate synthase. However, no
8
3
†
CCDC 893825 and 893826. For crystallographic data in CIF or other electronic
format see DOI: 10.1039/c3dt32901a
detailed analysis of this special coordination type outside an
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enzyme is available yet. Herein we describe the mixed sugar- perrhenate was dissolved. After adding a solution of triphenyl-
core–phosphate chelation of D-fructose 1,6-bisphosphate and phosphane (15.74 g, 60.00 mmol) in hot ethanol (40 mL at
its model glycerol 1-phosphate using the metal fragments 60 °C), the clear solution immediately turned into a green-
V
V
Re O(tmen) and Re O(phen) (tmen = N,N,N′,N′-tetramethyl- yellow suspension. After 1/2 h of reflux, a yellow solid of trans-
ethane-1,2-diamine; phen 1,10-phenanthroline). Many [ReOCl (PPh ) ] was filtered off and washed twice with hot
=
3
3 2
V
studies on the Re O fragment have been conducted in the last ethanol and acetone. The yield was 7.52 g (90%). Anal. calcd
1
1–13
few years,
3 2
most of them dealing with the medical signifi- for C36H31Cl OP Re: C, 51.90; H, 3.63; Cl, 12.77. Found: C,
cance of its complexes in the field of radiopharmacy. A few 52.02; H, 3.66; Cl, 12.35.
V
3
2,3,P1
studies on Re O complexes with sugars or sugar analogues are
Preparation of Na[ReO(tmen)(β-D-Fru2,3H−21,6P
2
H
2
-κ O
)]
1
2,13
also available.
(Na-1). Trisodium D-fructose 1,6-bisphosphate octahydrate
On an experimental basis, we used recently published find- (176 mg, 0.50 mmol), trans-[ReOCl (PPh ) ] (418 mg,
3
3 2
V
ings on the NMR-spectroscopic trace of Re O–carbohydrate 0.50 mmol), N,N,N′,N′-tetramethylethane-1,2-diamine (75.0 μL,
1
2–15
V
chelation.
coordination-induced shift’ (CIS) of about 20 ppm to the
NMR signals of those carbon atoms bound to Re-coordinating tion. After the solvent was removed, the blue residue of Na-1
Specifically, the Re centre entails a marked 0.50 mmol), and NEt
3
(208 μL, 1.50 mmol) in 250 mL metha-
1
3
‘
C
nol were stirred at RT for 48 hours, yielding a clear blue solu-
1
2
4
oxygen atoms. Taken together with structural information was washed with acetone and dissolved in methanol-d for
3
3
derived from J
and J coupling constants as well as X-ray NMR investigation.
P,H
results on model compounds, the mixed sugar-core–phosphate
H,H
3
2,3,P
Preparation of [ReO(tmen)(rac-Glyc2,3H−21PH-κ O
)]·
2 2
chelation of a metal centre by a sugar phosphate was compre- 2H O (2·2H O). Disodium rac-glycerol 1-phosphate hydrate
hensively analysed.
(108 mg, 0.50 mmol), trans-[ReOCl (PPh ) ] (418 mg,
3
3 2
0.50 mmol), N,N,N′,N′-tetramethylethane-1,2-diamine (75.0 μL,
0
.50 mmol), and NEt (139 μL, 1.00 mmol) in 250 mL metha-
3
Experimental
Methods and materials
nol were stirred at RT for 48 hours, yielding a clear blue solu-
tion. After the solvent was removed, the blue residue was
dissolved in acetone (40 mL). Colourless crystals of by-pro-
ducts such as triphenylphosphane were formed within 1 hour
at RT. After the colourless crystals were removed by filtration,
All chemicals were purchased and used without further purifi-
cation: ammonium perrhenate (ABCR), triphenylphosphane
(
Acros),
Aldrich), 1,10-phenanthroline (Aldrich), deuterium oxide,
methanol-d (Eurisotop), trisodium D-fructose 1,6-bisphos-
N,N,N′,N′-tetramethylethane-1,2-diamine
(Sigma-
blue crystals of 2·2H
amount of further colourless crystals of by-products within
hours at RT. The crystals were dissolved in D O for NMR
2
O were formed together with a small
4
5
2
phate octahydrate (Applichem), disodium rac-glycerol 1-phos-
phate hydrate (TCI Europe), triethylamine (Riedel-de Haën),
acetone, ethanol, methanol (Fluka).
investigation. The yield of the mixture of blue and colourless
crystals was 75 mg (ca. 5 mg of by-product). Due to the fact
that the blue product crystals were compounded with a small
amount of colourless crystals of by-products, an elementary
analysis was not conducted.
NMR spectroscopy
3
2,3,P
NMR spectra were recorded at 4 °C on Jeol ECX400/ECP 400
Preparation of [ReO(phen)(rac-Glyc2,3H−21PH-κ O
)]·
1
13
1
31
(
H: 400 MHz; C{ H}: 100 MHz; P: 109 MHz) spectrometers.
MeOH (3·MeOH). Disodium rac-glycerol 1-phosphate hydrate
Shift differences are given as δ(Ccomplex) − δ(Cfree sugar). The
(
108 mg, 0.50 mmol), trans-[ReOCl (PPh ) ] (418 mg,
3 3 2
values for the free glycose phosphate or glycerol phosphate
0.5 mmol), 1,10-phenanthroline (90.1 mg, 0.5 mmol), and
were taken from measurements in D O and were thus in
neutral aqueous solution.
2
NEt (138.6 μL, 1.0 mmol) in 250 mL methanol were stirred at
RT for 48 hours, yielding a clear yellow-brown solution. After
3
the solvent was removed, the brown residue was washed with
acetone and completely redissolved in methanol (80 mL).
The H, P{ H} and C{ H} NMR signals were assigned by Green crystals of 3·MeOH were formed together with a small
H– H COSY45, H– C HMQC, and P– H-HETCOR exper- amount of colourless crystals of by-products such as triphenyl-
iments in D O. To assign these signal sets to individual phosphane within 2 weeks at 4 °C. The yield of the mixture of
Species assignment
1
31
1
13
1
1
1
1
13
31
1
2
species, first of all, coupling constants J were analysed by green and colourless crystals was 71 mg (ca. 5 mg of by-
applying a modified Karplus relationship to identify the product). Due to the fact that the green product crystals were
1
6
correct anomer. Afterwards, CIS values were used to assign compounded with a small amount of colourless crystals of
the correct chelation site.
by-products, an elementary analysis was not conducted.
1
Analytical data of product complexes. Na-1:
CD
H
NMR
23.8
Syntheses
(
3
OD): δ [ppm] = 5.32–5.53 (m, 3H, H5, H6a, H6b), 5.41 (t,
3
3
3
Preparation of trans-[ReOCl (PPh ) ]. The preparation was 1H, H4, J 6.7 Hz, J 7.3 Hz), 5.77 (dd, 1H, H1a, J
1a,P
based on a published procedure. Ammonium perrhenate Hz, J1a,1b 11.2 Hz), 5.99 (dd, 1H, H1b, J1b,P 7.9 Hz), 6.11 (d,
3
3 2
7
3,4
4,5
1
2
3
+
+
(
(
2.68 g, 10.0 mmol) and concentrated hydrochloric acid 1H, H3). MS (FAB ): m/z = 656.8 [M − Na + 2H] , 678.7
20 mL) were heated in ethanol (100 mL) under reflux until the [M + H] , 700.7 [M + Na] , 757.8 [M − Na + 2H + NEt ] , 772.8
+
+
+
3
5
750 | Dalton Trans., 2013, 42, 5749–5754
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+
−
−
13
31
[
[
M − Na + 2H + tmen] . MS (FAB ): m/z = 676.8 [M − H] , 654.8 Table 1
C and P NMR chemical shifts (δ/ppm); Δδ is the difference of a
−
−
−
shift in the presence of the metal probe and the free D-fructose 1,6-bisphos-
phate or glycerol 1-phosphate, respectively. Bold-printed Δδ values indicate the
metal-binding site.
M − Na] , 560.7 [M − H − tmen] , 538.7 [M − Na − tmen] .
1
3
2·2H
2
2
O: H NMR (D
2
O): δ [ppm] = 3.91 (dd, 1H, H3a, J2,3
6
.2 Hz, J3a,3b 10.3 Hz), 4.56 (d, 1H, H3b), 4.61–4.76 (m, 3H,
H1a, H1b, H2). MS (FAB ): m/z = calculated for C H O N P
+
9
23 7 2
C1
C2
C3
C4
C5
C6
P1
0.1
P6
2.9
1
85
+
Re [M + H] : 487.0773, found 487.0726, calculated for
1
87
+
1
2
δ
Δδ
δ
72.5 122.6 104.1 75.9 85.2 67.6
C
9
H
3
23
O
7
N
2
P
Re [M + H] : 489.0801, found 489.0803.
6.5
73.0
7.7
21.1
90.6
18.6
28.1
87.6
24.7
1.4
5.1
2.2 −3.7 −0.8
+
185
·MeOH: MS (FAB ): m/z = calculated for C H O N P Re
1
5
15
7
2
0.2
+
[M
+
H] : 551.0147, found 551.0163, calculated for
Δδ
−5.7
1
87
+
C
15
H
15
O
7
N
2
P
Re [M + H] : 553.0175, found 553.0220.
atoms of the sugar core. Hence, the CIS values of about 21 and
8 ppm were close to the range of the CIS values for diolato
2
V
12
Re O complexes of methyl glycosides (19–26 ppm). Moreover,
Results and discussion
the coordination of the phosphate group at C1 was validated
1
31
The experimental setup was chosen to mimic the tridentate in a H-coupled P NMR spectrum. Here, the P1 signal was
3
1
1
bonding mode of D-fructose 1,6-bisphosphate as found in its found as a doublet of doublets with P– H coupling constants
III
V
complex with the Al (tacn) moiety (Scheme 1). Since the Re O of 23.8 and 7.9 Hz. The great difference between these two con-
fragment provides five vacant ligand-binding sites to complete stants verified that the phosphate group was in a fixed position
V
the octahedral structure of the target complex, two of the five due to the coordination to the Re O(tmen) fragment. In con-
1
31
positions were blocked by a spectator ligand. Preliminary tests trast, the H-coupled P NMR spectrum of the educt showed a
3
1
1
revealed the bidentate nitrogen chelator N,N,N′,N′-tetramethyl- triplet with P– H coupling constants between 3 and 5 Hz for
ethane-1,2-diamine (tmen) to be well-suited. The reaction of P1 indicating the free rotation of the phosphate group. Fur-
trans-[ReOCl (PPh ) ], tmen and D-fructose 1,6-bisphosphate in thermore, phosphate coordination was proven by a CIS value
3
3 2
3
1
31
methanol as the solvent and NEt
3
as the base to bind the of −3.7 ppm for the P NMR signal of P1. These P-NMR-
protons liberated from the sugar core’s hydroxy functions led spectroscopic findings were in agreement with the results on
to a clear blue solution. With the solvent removed, a blue mixed sugar-core–phosphate chelates of D-fructose 1,6-bisphos-
III
31
residue was obtained and analysed by mass spectroscopy. After phate with Al (tacn) (CIS value of P NMR signal: −6.7 ppm;
3
1
1
9
the residue was redissolved in methanol-d , a blue solution
P– H coupling constants: 24.4 and 4.7 Hz).
Mass-spectrometric analysis revealed the synthesised
NMR spectra are shown in Fig. 1. The C and P NMR chemi- complex to be the sodium salt of the [ReO(tmen)(β-D-Fruf2,3H−2
4
3
1
was obtained and analysed by NMR spectroscopy. The
P
1
3
31
-
3
2,3,P1 −
cal shifts of the resulting complex are given in Table 1.
1,6P
2
H
2
-κ O
)] (1) monoanion, Na-1 (Scheme 2).
3
The CIS values and the
JH,H coupling constants clearly
Since attempts to crystallise a salt of 1 failed, we extended
proved the coordination of β-D-fructofuranose 1,6-bisphos- the study to rac-glycerol 1-phosphate. As shown in Scheme 3,
V
phate to the Re O(tmen) fragment through the O2 and O3 glycerol 1-phosphate mimics that part of fructose 1,6-bisphos-
V
phate which coordinates to the Re O(tmen) fragment in 1.
In fact, the reaction of trans-[ReOCl (PPh ) ] with tmen and
3
3 2
rac-glycerol 1-phosphate in methanol–NEt
3
led to a clear blue
solution as well. With the solvent removed, a blue residue was
obtained and redissolved in acetone. After colourless crystals
of PPh
Glyc2,3H−21PH-κ O
3
had been removed, blue crystals of [ReO(tmen)(rac-
3
2,3,P
)]·2H O (2·2H O) were formed (Fig. 2).
2
2
Crystal-structure analysis (Table 2) showed that the lengths of
the Re–N and Re–O bonds were in the same range as the bond
31
1
31
Fig. 1 The P{ H} NMR spectrum (top) and the P NMR spectrum (bottom)
of the blue residue obtained by evaporating the reaction solution containing
3
2,3,P1 −
the product complex anion [ReO(tmen)(Fruf2,3H−21,6P
2
H
2
-κ O
)] (1) in
31
1
3
methanol-d
4
with P– H NMR coupling constants ( JP,H/Hz).
Scheme 2 The formula of 1.
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Table 2 Crystal-structure analyses
2
2·2H O
3·MeOH
Net formula
C
9
H
26
N
2 9
O PRe
16 18 2 8
C H N O Pre
583.504
/g mol−
1
523.492
M
r
Crystal size/mm
T/K
Radiation
Diffractometer
Crystal system
Space group
a/Å
0.13 × 0.10 × 0.03
173(2)
Mo-Kα
KappaCCD
Monoclinic
0.11 × 0.07 × 0.02
173(2)
Mo-Kα
Oxford XCalibur
Monoclinic
1
P2 /c
1
P2 /c
14.1114(5)
7.5592(5)
16.5961(5)
111.0465(5)
1652.22(13)
4
10.2979(5)
9.0749(5)
19.4763(7)
91.399(3)
1819.56(14)
4
b/Å
c/Å
Scheme 3 Glycerol 1-phosphate and fructose 1,6-bisphosphate chelation in
V
complexes with the Re O(tmen) fragment.
β(°)
3
V/Å
Z
D
μ/mm
−
3
c
/g cm
2.10454(17)
7.496
2.13006(16)
6.816
−
1
Absorption correction
Transmission factor range
Refls measured
Multi-scan
0.411–0.799
27 719
Multi-scan
0.570–0.873
6341
R
int
0.0501
0.0837
Mean σ(I)/I
θ range
Observed refls
x, y(weighting scheme)
Refls in refinement
Parameters
0.0330
3.15–27.61
3372
0.0029, 6.6091
3808
220
0.1187
4.18–26.31
2717
0.0093, 0
3673
258
Restraints
6
1
R(Fobs
)
0.0267
0.0549
1.089
0.0474
0.1017
0.938
2
R
S
w
(F )
Shift/errormax
Max electron density/e Å
Min electron density/e Å−
0.001
1.834
−1.116
0.001
2.571
−2.382
−
3
a
3
a
The maximum electron density is located at a distance of 0.98 Å
to Re.
3
2,3,P
Fig. 2 Molecular structure of [ReO(tmen)(rac-Glyc2,3H−21PH-κ O
crystals of the dihydrate (50% probability ellipsoids). Distances (Å) and angles
°): from Re1 to: O2 1.941(3), O3 1.954(3), O4 2.067(3), O7 1.678(3), N1
)] (2) in
(
2
1
.230(4), N2 2.224(4); from P1 to: O1 1.587(3), O4 1.528(3), O5 1.558(3), O6
.483(3); O2–Re1–O3 82.26(13), O2–Re1–O4 85.24(12), O3–Re1–O4 88.40(12),
O2–Re1–O7 106.18(14), O3–Re1–O7 101.51(14), N1–Re1–N2 81.69(15);
O2–C2–C3–O3: −37.9(5). The O5H group forms a short hydrogen bond (O5⋯O91
2
.522(5)) to one of the water molecules.
V
lengths found in crystal structures of methyl glycoside–Re O
1
2
complexes.
Regarding the Re–O(phosphate) bond, one
should note that no other crystal structure containing a phos-
V
phate group coordinating to a Re O centre is available yet. The
only similar crystal structure available was the one of a diester
V
18
of phosphoric acid coordinating to a Re O centre. Here, the
1
3
3 2,3,P
P
Fig. 3
C NMR spectrum of [ReO(tmen)(rac-Glyc2,3H−21PH-κ O
)] (2) in
Re–O distance amounted to 1.988(4) Å, shorter than the value
D
2
O measured at 4 °C.
determined for 2.
2
In the crystals of 2·2H O, the phosphate group was mono-
protonated just as the phosphate groups in the fructose 1,6- spectrum is shown in Fig. 3. The C and P NMR chemical
bisphosphate complex were in terms of mass spectrometry. shifts are given in Table 1.
1
3
31
Mass-spectrometric analysis of 2 confirmed the crystallo-
graphic result by showing signals only for the mono-proto- graphically determined κ O ,O coordination of glycerol
The CIS values found were in agreement with the crystallo-
2
2
3
V
nated form. Solutions of the blue crystals of 2 in D O (pH ∼ 5) 1-phosphate to the Re O(tmen) moiety. The coordination of the
2
1
3
were investigated by NMR spectroscopy. The
C
NMR phosphate group was characterised by a doublet of doublets in
5
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spectroscopic characteristics of the tridentate mode of this
bonding type were analysed by X-ray diffraction, various NMR
V
techniques and mass spectrometry by using Re O(N
2
) metal
2
fragments as the probes (N = tmen, phen). Experiments with
the D-fructose 1,6-bisphosphate model rac-glycerol 1-phosphate
confirmed the extension of the stable five-membered chelates
as found in analogous methyl-glycoside complexes by seven-
membered, phosphate-containing chelate rings. Hence, 2 and
3
are the first crystalline complexes that feature this special
coordination pattern. The close similarity of the NMR-spectro-
scopic and mass-spectrometric results on both D-fructose 1,6-
bisphosphate and glycerol 1-phosphate chelates confirms the
similarity of the metal centres’ bonding situation in both
environments.
Acknowledgements
The authors thank Julia Janik and Jan Geldsetzer for contribut-
ing to this work during their research courses.
References
3
2,3,P
Fig. 4 Structure of [ReO(phen)(rac-Glyc2,3H−21PH-κ O
)] (3) in crystals of
the methanol adduct (50% probability ellipsoids). Distances (Å) and angles (°):
from Re1 to: O2 1.917(6), O3 1.957(6), O4 2.102(6), O7 1.690(6), N1 2.129(6),
N10 2.158(7); from P1 to: O1 1.583(6), O4 1.527(6), O5 1.490(7), O6 1.558(7);
O2–Re1–O3 82.7(3), O2–Re1–O4 88.2(2), O3–Re1–O4 85.5(2), O2–Re1–O7
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stants of 23.8 and 6.9 Hz. Furthermore, the phosphate coordi-
nation caused a CIS value for the P NMR signal of −5.7 ppm.
The similarity of these values with the results of the D-fructose
,6-bisphosphate experiments is obvious.
Further evidence that the mixed sugar-core–phosphate
bonding mode can be reliably addressed was obtained with
,10-phenanthroline (phen) as the spectator ligand. Though
3
1
1
1
phen proved unsuitable in terms of the solubility of the obtained
products as a prerequisite for NMR analysis, another crystal-
structure analysis succeeded (Table 2). Hence, green crystals of
7 J. Akana, A. A. Fedorov, E. Fedorov, W. R. P. Novak,
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3
2,3,P
[
ReO(phen)(rac-Glyc2,3H−21PH-κ O
)]·MeOH (3·MeOH) were
(PPh ] with phen,
rac-glycerol 1-phosphate in methanol–NEt (Fig. 4).
isolated from a solution of trans-[ReOCl
3
3 2
)
3
Again, the phosphate group was found to be mono-proto-
nated by high-resolution mass spectroscopy. Furthermore, the 10 M. Steinborn, K. Breitruck and P. Klüfers, unpublished.
similarity of the two crystal structures was obvious in terms of 11 See, for example: (a) G. Pathuri, A. F. Hedrick, B. C. Disch,
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J. T. Doan, M. A. Ihnat, V. Awasthi and H. Gali, Bioconjugate
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Conclusions
Mixed sugar-core–phosphate chelation may be considered as
an initial bonding mode of D-fructose 1,6-bisphosphate to a
metal centre close to the physiological pH. The metrical and
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