organic compounds
4,5,6-Tri-O-acetyl-2,3-di-S-ethyl-2,3-dithio-D-allose diethyl dithioacetal
aSchool of Chemical Engineering and Environment, Beijing Institute of Technology, Beijing 100081, People's Republic of China, and bSchool of Science, Beijing Institute of Technology, Beijing 100081, People's Republic of China
*Correspondence e-mail: qpwu@bit.edu.cn
The title compound, C20H36O6S4, was obtained by ethanethiolysis of 3,5,6-tri-O-acetyl-1,2-O-isopropylidene-α-D-glucofuranose. One of the ethyl groups is disordered over two sites with refined occupancies of 0.869 (6) and 0.131 (6). Compared with the precursor, the of the stereocenters at positions C-3 and C-2 are inverted and maintained, respectively.
Related literature
For the bioactiviy of et al. (2007); Merino et al. (2008). For the structure of the precursor, 3,5,6-tri-O-acetyl-1,2-O-isopropylidene-α-D-glucofuranose, see: Wu et al. (2009). For related structures, see: Bethel & Ferrier (1972); Berrang & Hortor (1970); Divjaković et al. (1992).
see: ZhangExperimental
Crystal data
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Data collection: CrystalClear (Rigaku/MSC, 2005); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536809015694/lh2804sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809015694/lh2804Isup2.hkl
ZnBr2 (0.54 g, 2.4 mmol) was added to a solution of 3,5,6-tri-O-acetyl-1,2-O-isopropylidene-α-D-glucofuranose (0.67 g, 2.0 mmol) and ethanethiol (0.78 ml, 10 mmol) in dry CH2Cl2 (10 ml). After 5 h, saturated aqueous solution of NaHCO3 (20 ml) was added and separated. The organic layer was washed with brine, dried with MgSO4 and concentrated under reduced pressure. The residue was isolated through short on silica gel, which was eluded with EtOAc-petroleum to give the target compound (0.78 g, 78%). M. p. 62°, 1H-NMR(CDCl3, p.p.m.): 1.28 (m, 12 H), 2.06 (m, 9 H), 2.75 (m, 8 H), 3.07 (dd, 1 H), 3.48 (dd, 1 H), 4.20 (m, 1 H), 4.49 (dd, 1 H), 4.6 4 (d, 1 H), 5.54 (m, 1 H), 5.89 (dd, 1 H); 13C-NMR(CDCl3, p.p.m.):14.60, 14.74, 14.85, 14.92, 15.02, 21.23, 21.27, 25.79, 26.39, 28.31, 30.24, 51.47, 57.30, 57.48, 62.56, 71.96, 72.78, 169.19, 169.61, 170.82; HRMS (EI) m/z calculated for C20H36O6S4 500.13, found 500.14.
50 mg of the obtained product was dissolved in petroleum ether (5 ml) and the solution was kept at room temperature for 2 days to give colorless single crystals.
C—H were included in the riding model approximation with C—H distances 0.98–1.00 Å, and with Uiso=1.2Ueq(C) or 1.5Ueq(Cmethyl).
One of the ethyl groups is disordered over two sites with refined occupancies of 0.869 (6) and 0.131 (6). The restained distance of C13—C14 refined to 1.513 (4)Å and C13'-C14' refined to 1.502 (19) Å.
Data collection: CrystalClear (Rigaku/MSC, 2005); cell
CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. Molecular structure of the title compound with thermal displacement ellipsoids drawn at the 30% probability level. Open bonds show the disorder component. |
C20H36O6S4 | F(000) = 536 |
Mr = 500.73 | Dx = 1.302 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: P 2yb | Cell parameters from 4760 reflections |
a = 8.3395 (12) Å | θ = 2.2–27.9° |
b = 16.726 (2) Å | µ = 0.40 mm−1 |
c = 9.2027 (14) Å | T = 113 K |
β = 95.772 (5)° | Block, colorless |
V = 1277.2 (3) Å3 | 0.26 × 0.20 × 0.18 mm |
Z = 2 |
Rigaku Saturn diffractometer | 6060 independent reflections |
Radiation source: rotating anode | 5802 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.032 |
Detector resolution: 14.63 pixels mm-1 | θmax = 27.9°, θmin = 2.2° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | k = −21→22 |
Tmin = 0.902, Tmax = 0.931 | l = −12→12 |
16052 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.0326P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
6060 reflections | Δρmax = 0.20 e Å−3 |
298 parameters | Δρmin = −0.29 e Å−3 |
23 restraints | Absolute structure: Flack (1983), 2919 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (4) |
C20H36O6S4 | V = 1277.2 (3) Å3 |
Mr = 500.73 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.3395 (12) Å | µ = 0.40 mm−1 |
b = 16.726 (2) Å | T = 113 K |
c = 9.2027 (14) Å | 0.26 × 0.20 × 0.18 mm |
β = 95.772 (5)° |
Rigaku Saturn diffractometer | 6060 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 5802 reflections with I > 2σ(I) |
Tmin = 0.902, Tmax = 0.931 | Rint = 0.032 |
16052 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.066 | Δρmax = 0.20 e Å−3 |
S = 1.04 | Δρmin = −0.29 e Å−3 |
6060 reflections | Absolute structure: Flack (1983), 2919 Friedel pairs |
298 parameters | Absolute structure parameter: −0.03 (4) |
23 restraints |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.74081 (5) | −0.08494 (3) | 0.79166 (5) | 0.02103 (10) | |
S2 | 0.70511 (5) | 0.08746 (3) | 0.88989 (5) | 0.02203 (10) | |
S3 | 0.41930 (5) | 0.00547 (3) | 0.66199 (5) | 0.01940 (10) | |
S4 | 0.85901 (5) | 0.02564 (3) | 0.42590 (5) | 0.02148 (10) | |
O1 | 0.56270 (15) | −0.06561 (7) | 0.23706 (13) | 0.0182 (3) | |
O2 | 0.32000 (18) | −0.12020 (10) | 0.25917 (18) | 0.0405 (4) | |
O3 | 0.54225 (14) | 0.14186 (7) | 0.33931 (12) | 0.0169 (3) | |
O4 | 0.68402 (15) | 0.21225 (8) | 0.18563 (14) | 0.0269 (3) | |
O5 | 0.25647 (13) | 0.10093 (8) | 0.19236 (13) | 0.0209 (3) | |
O6 | 0.26208 (18) | 0.22570 (8) | 0.10243 (18) | 0.0378 (4) | |
C1 | 0.74322 (19) | 0.02080 (11) | 0.74033 (17) | 0.0171 (3) | |
H1 | 0.8521 | 0.0336 | 0.7099 | 0.021* | |
C2 | 0.61765 (18) | 0.03465 (11) | 0.60845 (18) | 0.0156 (3) | |
H2 | 0.6143 | 0.0933 | 0.5873 | 0.019* | |
C3 | 0.66042 (18) | −0.00888 (10) | 0.46908 (17) | 0.0147 (3) | |
H3 | 0.6708 | −0.0670 | 0.4933 | 0.018* | |
C4 | 0.53286 (19) | −0.00125 (11) | 0.33657 (17) | 0.0148 (3) | |
H4 | 0.4224 | −0.0068 | 0.3689 | 0.018* | |
C5 | 0.5413 (2) | 0.07353 (10) | 0.24304 (18) | 0.0164 (4) | |
H5 | 0.6440 | 0.0727 | 0.1957 | 0.020* | |
C6 | 0.3999 (2) | 0.08169 (12) | 0.12490 (18) | 0.0202 (4) | |
H6A | 0.4227 | 0.1244 | 0.0554 | 0.024* | |
H6B | 0.3843 | 0.0309 | 0.0700 | 0.024* | |
C7 | 0.8968 (2) | −0.08772 (14) | 0.94224 (19) | 0.0284 (4) | |
H7A | 0.8763 | −0.0444 | 1.0112 | 0.034* | |
H7B | 0.8888 | −0.1391 | 0.9944 | 0.034* | |
C8 | 1.0684 (2) | −0.07889 (15) | 0.9010 (3) | 0.0398 (5) | |
H8A | 1.0926 | −0.1230 | 0.8366 | 0.060* | |
H8B | 1.1441 | −0.0801 | 0.9896 | 0.060* | |
H8C | 1.0788 | −0.0279 | 0.8503 | 0.060* | |
C9 | 0.8906 (2) | 0.14400 (14) | 0.9124 (2) | 0.0311 (5) | |
H9A | 0.8924 | 0.1759 | 1.0031 | 0.037* | |
H9B | 0.9821 | 0.1061 | 0.9247 | 0.037* | |
C10 | 0.9154 (3) | 0.19954 (14) | 0.7876 (3) | 0.0395 (5) | |
H10A | 0.9222 | 0.1683 | 0.6984 | 0.059* | |
H10B | 1.0155 | 0.2297 | 0.8104 | 0.059* | |
H10C | 0.8245 | 0.2368 | 0.7729 | 0.059* | |
C11 | 0.2932 (2) | 0.08823 (13) | 0.59307 (19) | 0.0237 (4) | |
H11A | 0.3106 | 0.0975 | 0.4896 | 0.028* | |
H11B | 0.1789 | 0.0730 | 0.5962 | 0.028* | |
C12 | 0.3242 (2) | 0.16570 (13) | 0.6765 (2) | 0.0302 (5) | |
H12A | 0.2985 | 0.1585 | 0.7773 | 0.045* | |
H12B | 0.2561 | 0.2080 | 0.6296 | 0.045* | |
H12C | 0.4378 | 0.1806 | 0.6766 | 0.045* | |
C13 | 0.9482 (3) | −0.06248 (16) | 0.3541 (3) | 0.0317 (8) | 0.869 (6) |
H13A | 0.8677 | −0.0883 | 0.2826 | 0.038* | 0.869 (6) |
H13B | 1.0406 | −0.0461 | 0.3013 | 0.038* | 0.869 (6) |
C14 | 1.0059 (4) | −0.1230 (2) | 0.4699 (3) | 0.0428 (9) | 0.869 (6) |
H14A | 1.0905 | −0.0991 | 0.5378 | 0.064* | 0.869 (6) |
H14B | 1.0490 | −0.1700 | 0.4233 | 0.064* | 0.869 (6) |
H14C | 0.9154 | −0.1392 | 0.5235 | 0.064* | 0.869 (6) |
C13' | 0.9867 (15) | −0.0625 (8) | 0.4615 (17) | 0.024 (5) | 0.131 (6) |
H13C | 1.0967 | −0.0488 | 0.4379 | 0.029* | 0.131 (6) |
H13D | 0.9937 | −0.0741 | 0.5674 | 0.029* | 0.131 (6) |
C14' | 0.935 (2) | −0.1377 (8) | 0.381 (2) | 0.036 (4) | 0.131 (6) |
H14D | 0.8573 | −0.1665 | 0.4339 | 0.054* | 0.131 (6) |
H14E | 1.0297 | −0.1717 | 0.3722 | 0.054* | 0.131 (6) |
H14F | 0.8855 | −0.1240 | 0.2827 | 0.054* | 0.131 (6) |
C15 | 0.4443 (2) | −0.12014 (11) | 0.20382 (19) | 0.0200 (4) | |
C16 | 0.4899 (3) | −0.17588 (12) | 0.0885 (2) | 0.0277 (4) | |
H16A | 0.4155 | −0.2214 | 0.0805 | 0.042* | |
H16B | 0.6000 | −0.1952 | 0.1143 | 0.042* | |
H16C | 0.4843 | −0.1477 | −0.0053 | 0.042* | |
C17 | 0.6157 (2) | 0.20907 (11) | 0.2941 (2) | 0.0209 (4) | |
C18 | 0.5959 (3) | 0.27634 (12) | 0.3979 (2) | 0.0326 (5) | |
H18A | 0.6485 | 0.3244 | 0.3644 | 0.049* | |
H18B | 0.6454 | 0.2617 | 0.4954 | 0.049* | |
H18C | 0.4810 | 0.2871 | 0.4021 | 0.049* | |
C19 | 0.2065 (2) | 0.17773 (11) | 0.1783 (2) | 0.0221 (4) | |
C20 | 0.0766 (2) | 0.19526 (13) | 0.2743 (2) | 0.0301 (5) | |
H20A | 0.1246 | 0.2033 | 0.3748 | 0.045* | |
H20B | 0.0012 | 0.1502 | 0.2712 | 0.045* | |
H20C | 0.0187 | 0.2437 | 0.2397 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0232 (2) | 0.0209 (2) | 0.0183 (2) | −0.00083 (19) | −0.00179 (18) | 0.00364 (18) |
S2 | 0.0236 (2) | 0.0275 (2) | 0.0155 (2) | −0.00207 (19) | 0.00384 (17) | −0.00323 (19) |
S3 | 0.0155 (2) | 0.0251 (2) | 0.0183 (2) | −0.00173 (18) | 0.00489 (16) | 0.00091 (18) |
S4 | 0.01363 (19) | 0.0294 (3) | 0.0218 (2) | −0.00129 (18) | 0.00362 (16) | 0.00257 (19) |
O1 | 0.0183 (6) | 0.0201 (7) | 0.0166 (6) | −0.0007 (5) | 0.0034 (5) | −0.0072 (5) |
O2 | 0.0312 (8) | 0.0411 (9) | 0.0523 (10) | −0.0176 (7) | 0.0194 (7) | −0.0234 (8) |
O3 | 0.0213 (6) | 0.0138 (6) | 0.0157 (6) | −0.0013 (5) | 0.0026 (5) | 0.0002 (5) |
O4 | 0.0221 (7) | 0.0292 (8) | 0.0298 (7) | −0.0023 (6) | 0.0050 (6) | 0.0102 (6) |
O5 | 0.0175 (6) | 0.0194 (7) | 0.0253 (7) | 0.0012 (5) | −0.0005 (5) | 0.0021 (5) |
O6 | 0.0368 (8) | 0.0244 (8) | 0.0556 (10) | 0.0038 (6) | 0.0209 (8) | 0.0118 (7) |
C1 | 0.0174 (8) | 0.0212 (9) | 0.0128 (8) | −0.0003 (7) | 0.0018 (6) | −0.0010 (7) |
C2 | 0.0128 (8) | 0.0171 (8) | 0.0167 (8) | −0.0016 (7) | 0.0006 (6) | −0.0001 (6) |
C3 | 0.0146 (8) | 0.0165 (9) | 0.0133 (8) | 0.0000 (7) | 0.0028 (6) | 0.0000 (7) |
C4 | 0.0153 (8) | 0.0159 (8) | 0.0132 (8) | 0.0026 (7) | 0.0009 (6) | −0.0056 (7) |
C5 | 0.0152 (8) | 0.0166 (9) | 0.0172 (9) | 0.0016 (7) | 0.0016 (6) | −0.0023 (7) |
C6 | 0.0209 (9) | 0.0257 (10) | 0.0138 (8) | 0.0023 (8) | 0.0011 (7) | −0.0024 (7) |
C7 | 0.0352 (10) | 0.0305 (11) | 0.0176 (9) | 0.0017 (9) | −0.0064 (8) | 0.0041 (9) |
C8 | 0.0276 (11) | 0.0400 (13) | 0.0482 (14) | 0.0029 (10) | −0.0139 (9) | 0.0012 (11) |
C9 | 0.0263 (10) | 0.0344 (12) | 0.0317 (11) | −0.0028 (9) | −0.0008 (8) | −0.0138 (9) |
C10 | 0.0338 (11) | 0.0283 (12) | 0.0586 (15) | −0.0064 (10) | 0.0160 (11) | −0.0079 (11) |
C11 | 0.0174 (8) | 0.0356 (11) | 0.0182 (9) | 0.0039 (8) | 0.0029 (7) | 0.0010 (9) |
C12 | 0.0293 (11) | 0.0346 (12) | 0.0271 (11) | 0.0066 (9) | 0.0041 (8) | −0.0036 (9) |
C13 | 0.0213 (12) | 0.0515 (18) | 0.0234 (15) | 0.0072 (11) | 0.0073 (10) | −0.0077 (11) |
C14 | 0.0442 (17) | 0.046 (2) | 0.0393 (18) | 0.0195 (14) | 0.0118 (13) | −0.0025 (14) |
C13' | 0.007 (7) | 0.045 (12) | 0.022 (10) | −0.005 (6) | 0.004 (6) | 0.002 (7) |
C14' | 0.032 (7) | 0.024 (7) | 0.050 (8) | 0.010 (6) | −0.009 (6) | −0.005 (6) |
C15 | 0.0265 (10) | 0.0197 (9) | 0.0138 (9) | −0.0023 (8) | 0.0025 (7) | −0.0008 (7) |
C16 | 0.0377 (11) | 0.0240 (10) | 0.0222 (10) | −0.0048 (9) | 0.0067 (8) | −0.0076 (8) |
C17 | 0.0155 (8) | 0.0178 (9) | 0.0281 (10) | 0.0003 (7) | −0.0037 (7) | 0.0074 (8) |
C18 | 0.0386 (12) | 0.0200 (10) | 0.0382 (13) | −0.0062 (9) | −0.0003 (10) | −0.0018 (8) |
C19 | 0.0166 (8) | 0.0230 (10) | 0.0253 (10) | 0.0003 (8) | −0.0043 (7) | 0.0008 (8) |
C20 | 0.0242 (10) | 0.0332 (12) | 0.0329 (12) | 0.0057 (9) | 0.0033 (8) | 0.0084 (9) |
S1—C7 | 1.8035 (18) | C9—C10 | 1.507 (3) |
S1—C1 | 1.8313 (19) | C9—H9A | 0.9900 |
S2—C9 | 1.807 (2) | C9—H9B | 0.9900 |
S2—C1 | 1.8238 (17) | C10—H10A | 0.9800 |
S3—C11 | 1.814 (2) | C10—H10B | 0.9800 |
S3—C2 | 1.8387 (16) | C10—H10C | 0.9800 |
S4—C13 | 1.806 (2) | C11—C12 | 1.515 (3) |
S4—C13' | 1.829 (13) | C11—H11A | 0.9900 |
S4—C3 | 1.8348 (16) | C11—H11B | 0.9900 |
O1—C15 | 1.357 (2) | C12—H12A | 0.9800 |
O1—C4 | 1.4510 (19) | C12—H12B | 0.9800 |
O2—C15 | 1.200 (2) | C12—H12C | 0.9800 |
O3—C17 | 1.365 (2) | C13—C14 | 1.513 (4) |
O3—C5 | 1.446 (2) | C13—H13A | 0.9900 |
O4—C17 | 1.199 (2) | C13—H13B | 0.9900 |
O5—C19 | 1.352 (2) | C14—H14A | 0.9800 |
O5—C6 | 1.439 (2) | C14—H14B | 0.9800 |
O6—C19 | 1.188 (2) | C14—H14C | 0.9800 |
C1—C2 | 1.539 (2) | C13'—C14' | 1.502 (19) |
C1—H1 | 1.0000 | C13'—H13C | 0.9900 |
C2—C3 | 1.547 (2) | C13'—H13D | 0.9900 |
C2—H2 | 1.0000 | C14'—H14D | 0.9800 |
C3—C4 | 1.541 (2) | C14'—H14E | 0.9800 |
C3—H3 | 1.0000 | C14'—H14F | 0.9800 |
C4—C5 | 1.524 (2) | C15—C16 | 1.491 (2) |
C4—H4 | 1.0000 | C16—H16A | 0.9800 |
C5—C6 | 1.527 (2) | C16—H16B | 0.9800 |
C5—H5 | 1.0000 | C16—H16C | 0.9800 |
C6—H6A | 0.9900 | C17—C18 | 1.496 (3) |
C6—H6B | 0.9900 | C18—H18A | 0.9800 |
C7—C8 | 1.524 (3) | C18—H18B | 0.9800 |
C7—H7A | 0.9900 | C18—H18C | 0.9800 |
C7—H7B | 0.9900 | C19—C20 | 1.495 (3) |
C8—H8A | 0.9800 | C20—H20A | 0.9800 |
C8—H8B | 0.9800 | C20—H20B | 0.9800 |
C8—H8C | 0.9800 | C20—H20C | 0.9800 |
C7—S1—C1 | 101.38 (9) | C9—C10—H10A | 109.5 |
C9—S2—C1 | 101.20 (9) | C9—C10—H10B | 109.5 |
C11—S3—C2 | 102.08 (8) | H10A—C10—H10B | 109.5 |
C13—S4—C13' | 32.2 (5) | C9—C10—H10C | 109.5 |
C13—S4—C3 | 103.66 (10) | H10A—C10—H10C | 109.5 |
C13'—S4—C3 | 103.3 (4) | H10B—C10—H10C | 109.5 |
C15—O1—C4 | 118.30 (13) | C12—C11—S3 | 114.35 (13) |
C17—O3—C5 | 116.06 (13) | C12—C11—H11A | 108.7 |
C19—O5—C6 | 115.63 (14) | S3—C11—H11A | 108.7 |
C2—C1—S2 | 110.29 (11) | C12—C11—H11B | 108.7 |
C2—C1—S1 | 108.94 (11) | S3—C11—H11B | 108.7 |
S2—C1—S1 | 112.86 (9) | H11A—C11—H11B | 107.6 |
C2—C1—H1 | 108.2 | C11—C12—H12A | 109.5 |
S2—C1—H1 | 108.2 | C11—C12—H12B | 109.5 |
S1—C1—H1 | 108.2 | H12A—C12—H12B | 109.5 |
C1—C2—C3 | 112.81 (13) | C11—C12—H12C | 109.5 |
C1—C2—S3 | 107.93 (11) | H12A—C12—H12C | 109.5 |
C3—C2—S3 | 112.69 (11) | H12B—C12—H12C | 109.5 |
C1—C2—H2 | 107.7 | C14—C13—S4 | 113.70 (19) |
C3—C2—H2 | 107.7 | C14—C13—H13A | 108.8 |
S3—C2—H2 | 107.7 | S4—C13—H13A | 108.8 |
C4—C3—C2 | 114.75 (13) | C14—C13—H13B | 108.8 |
C4—C3—S4 | 111.65 (11) | S4—C13—H13B | 108.8 |
C2—C3—S4 | 108.65 (11) | H13A—C13—H13B | 107.7 |
C4—C3—H3 | 107.1 | C14'—C13'—S4 | 117.0 (11) |
C2—C3—H3 | 107.1 | C14'—C13'—H13C | 108.0 |
S4—C3—H3 | 107.1 | S4—C13'—H13C | 108.0 |
O1—C4—C5 | 103.41 (12) | C14'—C13'—H13D | 108.0 |
O1—C4—C3 | 106.83 (13) | S4—C13'—H13D | 108.0 |
C5—C4—C3 | 116.60 (14) | H13C—C13'—H13D | 107.3 |
O1—C4—H4 | 109.9 | C13'—C14'—H14D | 109.5 |
C5—C4—H4 | 109.9 | C13'—C14'—H14E | 109.5 |
C3—C4—H4 | 109.9 | H14D—C14'—H14E | 109.5 |
O3—C5—C4 | 107.49 (13) | C13'—C14'—H14F | 109.5 |
O3—C5—C6 | 108.79 (13) | H14D—C14'—H14F | 109.5 |
C4—C5—C6 | 113.55 (14) | H14E—C14'—H14F | 109.5 |
O3—C5—H5 | 109.0 | O2—C15—O1 | 123.03 (17) |
C4—C5—H5 | 109.0 | O2—C15—C16 | 126.52 (18) |
C6—C5—H5 | 109.0 | O1—C15—C16 | 110.42 (15) |
O5—C6—C5 | 109.18 (13) | C15—C16—H16A | 109.5 |
O5—C6—H6A | 109.8 | C15—C16—H16B | 109.5 |
C5—C6—H6A | 109.8 | H16A—C16—H16B | 109.5 |
O5—C6—H6B | 109.8 | C15—C16—H16C | 109.5 |
C5—C6—H6B | 109.8 | H16A—C16—H16C | 109.5 |
H6A—C6—H6B | 108.3 | H16B—C16—H16C | 109.5 |
C8—C7—S1 | 115.40 (14) | O4—C17—O3 | 123.77 (18) |
C8—C7—H7A | 108.4 | O4—C17—C18 | 126.18 (18) |
S1—C7—H7A | 108.4 | O3—C17—C18 | 110.05 (15) |
C8—C7—H7B | 108.4 | C17—C18—H18A | 109.5 |
S1—C7—H7B | 108.4 | C17—C18—H18B | 109.5 |
H7A—C7—H7B | 107.5 | H18A—C18—H18B | 109.5 |
C7—C8—H8A | 109.5 | C17—C18—H18C | 109.5 |
C7—C8—H8B | 109.5 | H18A—C18—H18C | 109.5 |
H8A—C8—H8B | 109.5 | H18B—C18—H18C | 109.5 |
C7—C8—H8C | 109.5 | O6—C19—O5 | 124.29 (17) |
H8A—C8—H8C | 109.5 | O6—C19—C20 | 124.31 (18) |
H8B—C8—H8C | 109.5 | O5—C19—C20 | 111.37 (16) |
C10—C9—S2 | 114.64 (15) | C19—C20—H20A | 109.5 |
C10—C9—H9A | 108.6 | C19—C20—H20B | 109.5 |
S2—C9—H9A | 108.6 | H20A—C20—H20B | 109.5 |
C10—C9—H9B | 108.6 | C19—C20—H20C | 109.5 |
S2—C9—H9B | 108.6 | H20A—C20—H20C | 109.5 |
H9A—C9—H9B | 107.6 | H20B—C20—H20C | 109.5 |
C9—S2—C1—C2 | −119.35 (13) | S4—C3—C4—C5 | −39.69 (17) |
C9—S2—C1—S1 | 118.55 (11) | C17—O3—C5—C4 | 153.04 (14) |
C7—S1—C1—C2 | 178.77 (11) | C17—O3—C5—C6 | −83.62 (17) |
C7—S1—C1—S2 | −58.37 (11) | O1—C4—C5—O3 | −169.73 (12) |
S2—C1—C2—C3 | 169.79 (11) | C3—C4—C5—O3 | −52.85 (18) |
S1—C1—C2—C3 | −65.83 (15) | O1—C4—C5—C6 | 69.89 (16) |
S2—C1—C2—S3 | −65.04 (13) | C3—C4—C5—C6 | −173.23 (13) |
S1—C1—C2—S3 | 59.34 (13) | C19—O5—C6—C5 | 104.90 (17) |
C11—S3—C2—C1 | 134.39 (12) | O3—C5—C6—O5 | −48.42 (19) |
C11—S3—C2—C3 | −100.37 (12) | C4—C5—C6—O5 | 71.22 (18) |
C1—C2—C3—C4 | 176.29 (14) | C1—S1—C7—C8 | −71.74 (18) |
S3—C2—C3—C4 | 53.74 (17) | C1—S2—C9—C10 | 68.51 (17) |
C1—C2—C3—S4 | −57.96 (16) | C2—S3—C11—C12 | −71.05 (15) |
S3—C2—C3—S4 | 179.49 (9) | C13'—S4—C13—C14 | 18.1 (8) |
C13—S4—C3—C4 | −87.95 (15) | C3—S4—C13—C14 | −75.1 (2) |
C13'—S4—C3—C4 | −121.1 (5) | C13—S4—C13'—C14' | −38.2 (11) |
C13—S4—C3—C2 | 144.51 (13) | C3—S4—C13'—C14' | 56.4 (13) |
C13'—S4—C3—C2 | 111.4 (5) | C4—O1—C15—O2 | −4.4 (3) |
C15—O1—C4—C5 | −116.96 (15) | C4—O1—C15—C16 | 173.80 (15) |
C15—O1—C4—C3 | 119.46 (15) | C5—O3—C17—O4 | −3.9 (2) |
C2—C3—C4—O1 | −160.52 (13) | C5—O3—C17—C18 | 175.50 (14) |
S4—C3—C4—O1 | 75.30 (15) | C6—O5—C19—O6 | 8.6 (3) |
C2—C3—C4—C5 | 84.49 (17) | C6—O5—C19—C20 | −169.42 (14) |
Experimental details
Crystal data | |
Chemical formula | C20H36O6S4 |
Mr | 500.73 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 113 |
a, b, c (Å) | 8.3395 (12), 16.726 (2), 9.2027 (14) |
β (°) | 95.772 (5) |
V (Å3) | 1277.2 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.40 |
Crystal size (mm) | 0.26 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Rigaku Saturn diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2005) |
Tmin, Tmax | 0.902, 0.931 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16052, 6060, 5802 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.066, 1.04 |
No. of reflections | 6060 |
No. of parameters | 298 |
No. of restraints | 23 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.29 |
Absolute structure | Flack (1983), 2919 Friedel pairs |
Absolute structure parameter | −0.03 (4) |
Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors thank the National Science Foundation of China (30340070) and the Ministry of Science and Technology of China (2006 A A100216) for financial support.
References
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Nucleosides are important compounds due to their extensive bioactivity in antitumor and antivirus (Zhang et al., 2007, Merino et al., 2008). In the course of our studies in the synthesis of nucleoside analogues, an ethanethio substituted thioacetal product was obtained as ethanethiolysis of 3,5,6-tri-O-acetyl-1,2-O-isopropylidene-α-D-glucofuranose (Wu et al., 2009). The purpose of the structure determination was to establish the position of the substituents of the ethanethio groups and the molecular conformation of the title compound. In contrast to its precursor, the absolute configuration of C-3 and C-2 are inverted and maintained, respectively, which is similar to the documented results (Berrang & Hortor, 1970; Bethel & Ferrier, 1972), but disagrees with the molecular structure reported by Divjaković (Divjakovic et al., 1992). Both the molecular conformation and structure are consistent with our desired intermediates for the synthesis of the corresponding 2',3'-dideoxy-2',3'-dimercaptoribonucleosides.