J . Org. Chem. 1995,60,3139-3148
3139
Molecular Modeling, X-ray Diffraction, and 13C,77Se CP/MAS NMR Studies of Bis(2,3,4,6-tetra-0-acetyl-/3-D-g1ucopyranosyl) Diselenide and Disulfide Marek J. Potrzebowski,*,+Maria Michalska,*J Jarosiaw Blaszczyk,§ Michai W. Wieczorek,o Wodzimierz Ciesielski,' Slawomir Kaimierski,+ and January Pluskowski' Polish Academy of Sciences, Centre of Molecular and Macromolecular Studies, Sienkiewicza 112, 90-362 t b d i , Poland, Laboratory of Organic Chemistry, Institute of Chemistry, Medical Academy, Muszynskiego 1, 90-151 Ebdi, Poland, and Technical University of Ebdi, Institute of Technical Biochemistry, Stefanowskiego 4 110, 90-924 Ebdi, Poland Received January 3, 1995@
Bis(2,3,4,6-tetra-0-acety1-~-D-glucopyranosyl) diselenide (1)crystallized from methanol forms three polymorphs. Crystals la are orthorhombic, P212121, with a = 10.143(3), b = 14.413(2), c = 26.290(2) A,V = 3843(1) A3,Z = 4, and D,= 1.418 g/cm3. Refinement using 3682 observed reflections for 435 parameters gives R = 0.041. Crystals lb are orthorhombic, P21212, with a = 24.180(2), b = 14.0748(7), c = 5.578 (1)A,V = 1898.4(4)A3, Z = 2, and D, = 1.435 g/cm3. Refinement using 2054 reflections for 219 parameters gives R = 0.058. Crystals of bis(2,3,4,6-tetra-O-acetyl-P-~glucopyranosyl) disulfide (2) crystallized from methanol are orthorhombic, P212121, with a = 10.099(11, b = 14.207(2), c = 26.253(3) A,V = 3766(1) A3, Z = 4, and D,= 1.282 g/cm3. Refinement using 3438 reflections for 435 parameters gives R = 0.071. Diselenides la and lb have molecular structures with anti-syn and anti-anti arrangements of the C-C-Se-Se-C-C backbone. Changes of geometry influence the bond lengths and angles because of the strong hyperconjugative interaction between the p-electron lone pair of selenium and the U*C-C orbital. Molecular symmetry and molecular packing effects are studied by high-resolution solid-state 13C and 77SeNMR. The principal elements (6iJ of the 77Sechemical shift tensors for polymorphs 1 a-c, determined from spinning sideband intensities, are discussed in terms of local geometry. The structure of modification IC,which gave crystals of insufficient quality for XRD measurements, was deduced from molecular mechanics calculations and solid-state NMR.
Introduction Disulfide bonds play a n important role in the chemistry of natural products.lS2 The S-S linkage formed a t cysteine residues influences local conformation and stability in folded proteins and polypeptide^.^^^ Little attention has been paid to dichalcogenide bonds in saccharides, even though these compounds are significant in metabolism and are useful as models for structural ~ t u d i e s . Lees ~ , ~ and Whitesides reported that 6,6'-dithiosucrose cyclic disulfide is a convenient compound for the study of thiol-disulfide i n t e r ~ h a n g e .Circular ~ dichroism of monosaccharide dichalcogenides was measured by Michalska and Snatzke.8 Little is known about the nature of the seleniumselenium bond in saccharides. Simple selenoorganic compounds mimic in vitro the enzymatic activity of glutathione peroxidase, a n important system of cell
* Author to whom correspondence should be addressed. ' Polish Academy of Sciences.
Medical Academy. Technical University of t 6 d i . Abstract published in Advance ACS Abstracts, April 15, 1995. (1)Jocelyn, P. C. Biochemistry ofthe SH Group; Academic: London, 1972. (2)Huxtable, R. J . Biochemistry ofsulfur; Plenum: New York, 1987. (3)Creighton, S. BioEssays 1988,8,57. (4)Zeigler, D.H. Annu. Reu. Biochem. 1985,54, 305. ( 5 )Gilbert, H. F. Adv. Enzymol. 1990,63,69. (6)Bock, K.;Lemieux, R. U. Carbohydr. Res. 1982,100, 63-74. (7)Lees, W. J.; Whitesides, G. M. J . Am. Chem. SOC.1980,102, 1860- 1869. ( 8 ) Michalska, M.; Snatzke, G. Liebigs Ann. Chem. 1987,179-181. (9)Wilson, S. K.;Zucher, P. A,; Huang, R.-R. C.; Spector, A. J. Am. Chem. SOC.1989,111,5936-5939. (lO)Chance, B.; Boveris, A.; Nakase, Y.; Sies, H. Functions of Glutathione in Liver and Kidney; Springer-Verlag: Berlin, 1978;pp 95-106. 8
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defense against oxidative s t r e s ~ . ~The J ~ modified diary1 selenides and diselenides show significant glutathione peroxidase activity.11J2 As part of our continuing interest in the properties of sulfurhelenium systems in the solid tate el^-'^ we report X-ray Diffraction (XRD) and 13C and 77Semagic angle spinning with cross polarization (CP/MAS)results for bis(2,3,4,6-tetra-0-acetyl-P-~-glucopyranosyl) diselenide (1) and disulfide (2).We show that changes of geometry of the C-C-X-X-C-C backbone when X is in an anomeric position influence C-X bond lengths and C-C-X bond angles of B-D-glucopyranose rings because of the overlap of the p-electron lone pair of the X atom and the u*c1-c2 orbital of the sugar moiety. I3C and 77Sespectra are discussed in terms of crystal and molecular structures established from XRD studies. The relationship between 77Sespectral parameters and (11)Warin, V.; Guelzim, A.; Baert, F.; Galet, V.; Houssin, R.; Lesieur, D. Acta Crystallogr. 1993,C49, 2005-2007. (12) Parnham, M. J.;Graf, E. Biochem. Pharmocol. 1987,36,30953102. (13) Chu, P.-J.; Potrzebowski, M. J . Magn. Res. Chem. 1990,28, 477-485. (14)Potrzebowski, M. J. J. Chem. Soc., Perkin Trans. 2 1993,6366. (15) Potrzebowski, M. J.; Reibenspies, J . H.; Zhong, Z. Heteroatom Chem. 1991,2,455-460. (16)Knopik, P.;Luczak, L.; Potrzebowski, M. J.; Michalski, J.; Blaszczyk, J.; Wieczorek, M. W. J . Chem. SOC.Dalton Trans. 1993, 2749-2757. (17)Potrzebowski, M. J.; Grossman, G.; Blaszczyk, J.; Wieczorek, M. W.; Sieler, J.;Knopik, P.; Komber, H. Inorg. Chem., 1994,33,46884695. (18)Potrzebowski, M. J.;Michalski, J . 31PHigh-Resolution SolidState NMR Studies of Thiophosphoroorganic Compounds In Phosphorus31 NMR Spectra Properties in Compound Characterization and Structural Analysis; Quin, L. D., Verkade, J . G., Eds.; VCH: New York, 1994;Chapter 31,pp 413-426.
0022-326319511960-3139$09.00/00 1995 American Chemical Society
Potrzebowski e t al.
3140 J. O r g . Chem., Vol. 60, No. 10, 1995 Table 1. Crystal Data and Experimental Details compound la compound l b
compound 2
~
molecular formula crystallographicsystem space group
(A) (A) c (A) v (A3) z a b
D,(glcm3) p (cm-’)
crystal dimensions (mm) maximum 20 (deg) radiation, 1 (A) scan mode scan width (deg) hkl ranges
Cz~HssOleSez orthorhombic p212121 10.143(3) 14.413(2) 26.290(2) 3843(1) 4 1.418(2) 30.6 0.3, 0.3, 0.4 150 Cu Ka,1.54178 012e 0.95 0.14 tan e h=012 k=018 1=032
CzsHssOl~Sez orthorhombic P21212 24.180(2) 14.0748(7) 5.578(1) 1898.4(4) 2 1.435(2) 31.0 0.4,0.4,0.5 150 Cu Ka,1.54178 0128 0.82 0.14 tan e h=O30 k=017 1=06
CzsHssOisSz orthorhombic m2121 10.099(1) 14.207(2) 26.253(3) 3766(1) 4 1.282 18.6 0.25, 0.35, 0.4 150 Cu Ka,1.54178 0128 1.14 0.14 tan e h=-12O k = -17 0 l=032
1.00002 1.02618 1.01235
1.00003 1.02372 1.01073
1.00028 1.07594 1.03607
4122 3682 435 0.294 -0.539 0.041
2184 2054 219 0.545 -0.456 0.058
3944 3438 435 0.389 -0.408 0.071
DECAY correction: min max av no. of reflections: unique with Z 2 3dZ) no. of parameters refined largest diff. peak ( e k 3 ) largest diff. hole ( e k 3 ) R
+
the distortion of selenium local geometry is described. Finally, experimental geometric parameters are compared with calculated values. The usefulness of these methods in structural analysis of dichalcogen saccharides is discussed. Experimental Section Bis(2,3,4,6-tetra-O-acetyl-~-D-g~ucopyranosy~) diselenide (1) and disulfide (2) were synthesized according to established procedure^.'^ Diselenide 1 was dissolved in boiling methanol. The saturated solution was brought to ambient temperature and crystals l a were obtained. Crystals l b were grown from methanol a t -10 “C, and the sample was kept in refrigerator at -10 “C. Crystals l b and IC were obtained by isothermal evaporation of methanol at room temperature. Crystals 2 were crystallized from methanol at room temperature. X-ray Diffraction. Crystal and molecular structures of diselenides l a and l b and disulfide 2 were determined using a CAD4 diffractometer. All compounds crystallize in orthorhombic systems with space group P212121 for l a and 2 and P21212 for lb. Crystal data and experimental details are shown in Table 1. Intensity data were collected a t room temperature using a diffractometer with graphite-monochromatized Cu K a radiation. Lattice constants were refined by least-squares fit of 25 reflections in a e range of 17.6-23.9’ for l a , 21.4-26.2’ for lb, and 20.5-27.3O for 2. Declines in intensities of three standard reflections (2,5,-5; 3,6,1; 3,3,-10 for la, -10,-4,1; -3,-1,l; 3,6,2 for lb, and 2,2,-12; 4,-1,-7; 3,0,-10 for 2) were 5.0% during 69.8 h of exposure, 4.6% during 29.2 h and 13.6% during 65.0 h respectively for la, lb, and 2. Because of observed loss in intensities of reflections which was, on average, 0.072% per hour in l a , 0.137% per hour in l b and 0. 210% per hour in 2, experimental data of la, lb, and 2 were corrected using the DECAY program.20 A total of 3682, 2054, and 3438 observed reflections, respectively for la, lb, and 2 [with I 2 3d1)1, were used to solve the structures by direct methods and to refine it by full-matrix least-squares fits (19)(a) Wrede, F. Ber. Dtsch. Chem. Ges. 1919, 52, 1756. (b) Michalska, M.; Michalski, J.; Orlich, I. Tetrahedron 1978,14, 617622. (20) Frenz, B. A. SDP- Structure Determination Package; EnrafNonius, Delft, Holland, 1984.
+
+
using Fs. Hydrogen atoms were placed geometrically at idealized positions and set as riding, with fixed isotropic thermal parameters. Anisotropic thermal parameters were refined for all non-hydrogen atoms. The final refinement converged to R = 0.041 in la, R = 0.058 in lb, and R = 0.071 in 2 with respective weighting schemes w = l/[02(F) pF1, where p was 0.000259, 0.003388, and 0.000882, respectively. The absolute configuration was established by use of two independent methods: calculation of the Rogers’ parameter and the Hamilton test.21s22The obtained value of 17 for l a was equal t o 0.92(6), and vinv = 0.936(6) for structure with the “opposite”configuration. The results of the Hamilton test were N = 3247 and R-ratio= 1.0105, which gives the probability of the opposite structure of a < The results of the Hamilton test (N = 3003 and R-,ti, = 1.0020) showed that the “opposite” structure l b had to be rejected with very high probability (a
