Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802001952/dn6017sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802001952/dn6017Isup2.hkl |
CCDC reference: 182597
(III) was prepared conventionally from (I). Analysis of (III), found: C 53.69, H 6.74, S 7.31%; calculated: C 53.80, H 6.77, S 7.18%. [α]D -121° (cl, MeOH). Crystals from diethyl ether/hexane.
All H atoms were introduced at calculated positions as riding atoms (C—H = 0.97–0.98 Å, using AFIX 37 for CH3, AFIX 43 for aromatic CH and AFIX 13 for CH), with a displacement parameter equal to 1.2 (CH) or 1.5(CH3) times that of the parent atom. On the basis of 2259 Friedel pairs, final refinement allowed the fraction contribution of the inverted enantiomer to vary (Bernardinelli & Flack, 1985; Flack, 1983), the absolute structure parameter quoted being the refined value of this contribution.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft,1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTON92 (Spek, 1992) and PLATON92 (Spek, 1992); software used to prepare material for publication: SHELXL97.
C20H30O9S | Dx = 1.327 Mg m−3 |
Mr = 446.50 | Melting point = 130–131 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 9970 reflections |
a = 8.7709 (3) Å | θ = 3.0–28.3° |
b = 14.0181 (10) Å | µ = 0.19 mm−1 |
c = 18.1744 (13) Å | T = 150 K |
V = 2234.6 (2) Å3 | Needle, colourless |
Z = 4 | 0.25 × 0.10 × 0.05 mm |
F(000) = 952 |
Nonius KappaCCD area-detector diffractometer | 3591 reflections with I > 2σ(I) |
Radiation source: Enraf-Nonius FR591 rotating anode | Rint = 0.058 |
Graphite monochromator | θmax = 28.3°, θmin = 3.0° |
Detector resolution: 9.091 pixels/mm pixels mm-1 | h = −9→9 |
ϕ and ω scans to fill Ewald sphere | k = −18→18 |
9970 measured reflections | l = −24→24 |
5177 independent 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)] = 0.069 | H-atom parameters constrained |
wR(F2) = 0.122 | w = 1/[σ2(Fo2) + (0.0139P)2 + 2.7542P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.007 |
5177 reflections | Δρmax = 0.31 e Å−3 |
278 parameters | Δρmin = −0.33 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (12) |
C20H30O9S | V = 2234.6 (2) Å3 |
Mr = 446.50 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.7709 (3) Å | µ = 0.19 mm−1 |
b = 14.0181 (10) Å | T = 150 K |
c = 18.1744 (13) Å | 0.25 × 0.10 × 0.05 mm |
Nonius KappaCCD area-detector diffractometer | 3591 reflections with I > 2σ(I) |
9970 measured reflections | Rint = 0.058 |
5177 independent reflections |
R[F2 > 2σ(F2)] = 0.069 | H-atom parameters constrained |
wR(F2) = 0.122 | Δρmax = 0.31 e Å−3 |
S = 1.09 | Δρmin = −0.33 e Å−3 |
5177 reflections | Absolute structure: Flack (1983) |
278 parameters | Absolute structure parameter: 0.00 (12) |
0 restraints |
Experimental. Cell measurement fields are not particularly relevant to the area detector data. Entire data set used to refine cell. Cell indexed from a 10 ° phi range. |
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 | ||
C1 | 0.9738 (4) | 0.8151 (3) | 0.7892 (2) | 0.0220 (8) | |
H1 | 1.0716 | 0.8065 | 0.8144 | 0.031* | |
O1 | 0.9181 (3) | 0.90663 (19) | 0.80578 (15) | 0.0271 (7) | |
C2 | 0.8577 (4) | 0.7461 (3) | 0.8229 (2) | 0.0183 (8) | |
H2 | 0.8334 | 0.7654 | 0.8734 | 0.026* | |
O2 | 0.9276 (3) | 0.65154 (17) | 0.82271 (14) | 0.0192 (6) | |
C3 | 0.7152 (4) | 0.7450 (3) | 0.77667 (19) | 0.0173 (8) | |
H3 | 0.6634 | 0.8064 | 0.7829 | 0.024* | |
O3 | 0.6155 (3) | 0.6718 (2) | 0.80176 (13) | 0.0219 (6) | |
C4 | 0.7474 (4) | 0.7315 (3) | 0.69643 (19) | 0.0175 (8) | |
H4 | 0.7881 | 0.6673 | 0.6881 | 0.024* | |
O4 | 0.6060 (3) | 0.74243 (19) | 0.65738 (13) | 0.0192 (6) | |
C5 | 0.8603 (4) | 0.8054 (3) | 0.6682 (2) | 0.0209 (9) | |
H5 | 0.8157 | 0.8694 | 0.6717 | 0.029* | |
O5 | 0.9959 (3) | 0.79962 (19) | 0.71360 (13) | 0.0224 (6) | |
C6 | 0.9095 (5) | 0.7858 (3) | 0.5902 (2) | 0.0296 (10) | |
H6A | 0.9772 | 0.8354 | 0.5740 | 0.041* | |
H6B | 0.8216 | 0.7840 | 0.5588 | 0.041* | |
H6C | 0.9612 | 0.7255 | 0.5881 | 0.041* | |
C7 | 1.0310 (5) | 0.9802 (3) | 0.7969 (2) | 0.0361 (11) | |
H7A | 1.1088 | 0.9728 | 0.8336 | 0.051* | |
H7B | 0.9836 | 1.0416 | 0.8023 | 0.051* | |
H7C | 1.0757 | 0.9754 | 0.7488 | 0.051* | |
C14 | 0.4713 (4) | 0.6744 (3) | 0.7649 (2) | 0.0250 (9) | |
O14 | 0.3986 (3) | 0.7623 (2) | 0.78006 (16) | 0.0357 (8) | |
C15 | 0.3821 (5) | 0.7843 (4) | 0.8563 (2) | 0.0517 (16) | |
H15A | 0.3082 | 0.7422 | 0.8779 | 0.072* | |
H15B | 0.3486 | 0.8491 | 0.8616 | 0.072* | |
H15C | 0.4783 | 0.7763 | 0.8806 | 0.072* | |
C16 | 0.3834 (5) | 0.5883 (4) | 0.7926 (2) | 0.0420 (13) | |
H16A | 0.4377 | 0.5311 | 0.7801 | 0.059* | |
H16B | 0.2843 | 0.5871 | 0.7702 | 0.059* | |
H16C | 0.3726 | 0.5923 | 0.8451 | 0.059* | |
C17 | 0.4938 (4) | 0.6745 (3) | 0.6798 (2) | 0.0215 (9) | |
O17 | 0.5458 (3) | 0.58073 (18) | 0.66352 (14) | 0.0268 (6) | |
C18 | 0.5788 (5) | 0.5630 (3) | 0.5873 (2) | 0.0377 (12) | |
H18A | 0.4850 | 0.5573 | 0.5604 | 0.053* | |
H18B | 0.6359 | 0.5049 | 0.5829 | 0.053* | |
H18C | 0.6374 | 0.6150 | 0.5678 | 0.053* | |
C19 | 0.3490 (4) | 0.6998 (3) | 0.6390 (2) | 0.0276 (10) | |
H19A | 0.3701 | 0.7044 | 0.5873 | 0.039* | |
H19B | 0.3111 | 0.7598 | 0.6566 | 0.039* | |
H19C | 0.2739 | 0.6511 | 0.6473 | 0.039* | |
S21 | 0.96432 (11) | 0.60403 (7) | 0.89998 (5) | 0.0199 (2) | |
O22 | 1.0252 (3) | 0.67532 (19) | 0.94803 (14) | 0.0275 (7) | |
O23 | 1.0534 (3) | 0.52188 (19) | 0.88131 (15) | 0.0271 (7) | |
C24 | 0.7849 (4) | 0.5673 (3) | 0.9332 (2) | 0.0178 (8) | |
C25 | 0.7267 (4) | 0.4804 (3) | 0.9110 (2) | 0.0258 (9) | |
H25 | 0.7817 | 0.4413 | 0.8793 | 0.036* | |
C26 | 0.5846 (5) | 0.4522 (3) | 0.9369 (2) | 0.0283 (10) | |
H26 | 0.5445 | 0.3937 | 0.9223 | 0.040* | |
C27 | 0.5017 (4) | 0.5101 (3) | 0.9843 (2) | 0.0235 (9) | |
C28 | 0.5626 (4) | 0.5977 (3) | 1.0052 (2) | 0.0264 (9) | |
H28 | 0.5074 | 0.6374 | 1.0364 | 0.037* | |
C29 | 0.7049 (4) | 0.6266 (3) | 0.9801 (2) | 0.0232 (9) | |
H29 | 0.7456 | 0.6849 | 0.9946 | 0.032* | |
C30 | 0.3467 (5) | 0.4799 (4) | 1.0116 (3) | 0.0411 (12) | |
H30A | 0.2727 | 0.4891 | 0.9733 | 0.058* | |
H30B | 0.3192 | 0.5175 | 1.0537 | 0.058* | |
H30C | 0.3495 | 0.4137 | 1.0252 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.018 (2) | 0.025 (2) | 0.023 (2) | −0.0024 (18) | −0.0049 (17) | 0.0031 (17) |
O1 | 0.0286 (16) | 0.0200 (15) | 0.0328 (16) | −0.0066 (13) | −0.0034 (12) | −0.0007 (13) |
C2 | 0.016 (2) | 0.020 (2) | 0.019 (2) | 0.0024 (16) | −0.0028 (15) | 0.0006 (16) |
O2 | 0.0182 (15) | 0.0211 (14) | 0.0183 (13) | 0.0032 (11) | −0.0006 (10) | 0.0012 (11) |
C3 | 0.0121 (19) | 0.024 (2) | 0.0155 (19) | −0.0031 (16) | 0.0017 (15) | 0.0032 (16) |
O3 | 0.0147 (14) | 0.0331 (16) | 0.0179 (14) | −0.0053 (12) | −0.0019 (11) | 0.0057 (13) |
C4 | 0.016 (2) | 0.019 (2) | 0.0173 (19) | −0.0001 (15) | −0.0014 (15) | −0.0001 (16) |
O4 | 0.0151 (13) | 0.0245 (15) | 0.0181 (14) | −0.0025 (11) | −0.0041 (11) | 0.0022 (12) |
C5 | 0.017 (2) | 0.025 (2) | 0.021 (2) | −0.0016 (16) | −0.0018 (16) | 0.0037 (17) |
O5 | 0.0150 (15) | 0.0291 (16) | 0.0230 (14) | −0.0029 (11) | −0.0005 (11) | 0.0059 (12) |
C6 | 0.028 (2) | 0.040 (3) | 0.021 (2) | −0.0077 (19) | 0.0018 (18) | 0.0039 (19) |
C7 | 0.047 (3) | 0.027 (2) | 0.034 (2) | −0.016 (2) | −0.007 (2) | 0.007 (2) |
C14 | 0.017 (2) | 0.038 (2) | 0.020 (2) | −0.005 (2) | −0.0044 (17) | −0.0003 (17) |
O14 | 0.0210 (15) | 0.059 (2) | 0.0274 (17) | 0.0114 (15) | −0.0022 (13) | −0.0131 (15) |
C15 | 0.030 (3) | 0.093 (5) | 0.032 (3) | 0.010 (3) | −0.001 (2) | −0.027 (3) |
C16 | 0.027 (3) | 0.074 (4) | 0.025 (2) | −0.024 (3) | −0.0055 (19) | 0.009 (2) |
C17 | 0.020 (2) | 0.021 (2) | 0.024 (2) | −0.0048 (16) | −0.0003 (16) | −0.0018 (17) |
O17 | 0.0335 (16) | 0.0216 (15) | 0.0251 (15) | −0.0010 (13) | −0.0025 (13) | −0.0012 (11) |
C18 | 0.048 (3) | 0.033 (3) | 0.032 (3) | 0.007 (2) | 0.001 (2) | −0.011 (2) |
C19 | 0.021 (2) | 0.036 (3) | 0.025 (2) | −0.0054 (19) | −0.0008 (17) | −0.001 (2) |
S21 | 0.0172 (5) | 0.0205 (5) | 0.0221 (5) | −0.0008 (4) | −0.0030 (4) | 0.0032 (4) |
O22 | 0.0273 (16) | 0.0262 (15) | 0.0291 (15) | −0.0064 (13) | −0.0077 (13) | 0.0037 (12) |
O23 | 0.0228 (15) | 0.0238 (16) | 0.0347 (17) | 0.0039 (12) | −0.0017 (12) | 0.0037 (13) |
C24 | 0.016 (2) | 0.020 (2) | 0.018 (2) | −0.0004 (16) | −0.0014 (16) | 0.0041 (16) |
C25 | 0.029 (2) | 0.023 (2) | 0.025 (2) | −0.0006 (18) | 0.0019 (18) | −0.0046 (19) |
C26 | 0.032 (3) | 0.025 (2) | 0.029 (2) | −0.0075 (19) | −0.0011 (19) | 0.0041 (19) |
C27 | 0.019 (2) | 0.030 (2) | 0.022 (2) | −0.0023 (17) | 0.0022 (16) | 0.0062 (18) |
C28 | 0.028 (2) | 0.031 (2) | 0.020 (2) | 0.004 (2) | 0.0044 (16) | 0.0019 (18) |
C29 | 0.029 (2) | 0.022 (2) | 0.018 (2) | −0.0042 (17) | −0.0011 (17) | 0.0020 (17) |
C30 | 0.029 (3) | 0.058 (3) | 0.037 (3) | −0.008 (2) | 0.003 (2) | 0.012 (3) |
C1—O5 | 1.404 (4) | C14—C16 | 1.518 (6) |
C1—O1 | 1.406 (5) | C14—C17 | 1.559 (5) |
C1—C2 | 1.532 (5) | O14—C15 | 1.426 (5) |
O1—C7 | 1.439 (5) | C17—O17 | 1.422 (5) |
C2—O2 | 1.460 (4) | C17—C19 | 1.513 (5) |
C2—C3 | 1.506 (5) | O17—C18 | 1.436 (5) |
O2—S21 | 1.587 (3) | S21—O22 | 1.431 (3) |
C3—O3 | 1.423 (4) | S21—O23 | 1.432 (3) |
C3—C4 | 1.497 (5) | S21—C24 | 1.762 (4) |
O3—C14 | 1.432 (4) | C24—C29 | 1.382 (5) |
C4—O4 | 1.437 (4) | C24—C25 | 1.381 (5) |
C4—C5 | 1.522 (5) | C25—C26 | 1.389 (6) |
O4—C17 | 1.429 (4) | C26—C27 | 1.390 (6) |
C5—O5 | 1.449 (4) | C27—C28 | 1.392 (6) |
C5—C6 | 1.508 (5) | C27—C30 | 1.508 (5) |
C14—O14 | 1.414 (5) | C28—C29 | 1.389 (5) |
O5—C1—O1 | 113.5 (3) | C16—C14—C17 | 113.2 (3) |
O5—C1—C2 | 112.7 (3) | C14—O14—C15 | 115.1 (4) |
O1—C1—C2 | 105.0 (3) | O17—C17—O4 | 109.6 (3) |
C1—O1—C7 | 113.0 (3) | O17—C17—C19 | 112.6 (3) |
O2—C2—C3 | 109.7 (3) | O4—C17—C19 | 106.4 (3) |
O2—C2—C1 | 107.1 (3) | O17—C17—C14 | 104.3 (3) |
C3—C2—C1 | 109.5 (3) | O4—C17—C14 | 111.7 (3) |
C2—O2—S21 | 117.6 (2) | C19—C17—C14 | 112.3 (3) |
O3—C3—C4 | 109.7 (3) | C17—O17—C18 | 115.1 (3) |
O3—C3—C2 | 109.8 (3) | O22—S21—O23 | 120.18 (17) |
C4—C3—C2 | 112.8 (3) | O22—S21—O2 | 108.83 (15) |
C3—O3—C14 | 112.0 (3) | O23—S21—O2 | 103.80 (15) |
O4—C4—C3 | 107.8 (3) | O22—S21—C24 | 109.18 (17) |
O4—C4—C5 | 108.8 (3) | O23—S21—C24 | 109.47 (18) |
C3—C4—C5 | 111.4 (3) | O2—S21—C24 | 104.11 (15) |
C17—O4—C4 | 112.5 (3) | C29—C24—C25 | 121.5 (4) |
O5—C5—C6 | 106.8 (3) | C29—C24—S21 | 119.3 (3) |
O5—C5—C4 | 107.7 (3) | C25—C24—S21 | 119.2 (3) |
C6—C5—C4 | 112.3 (3) | C24—C25—C26 | 119.0 (4) |
C1—O5—C5 | 115.8 (3) | C25—C26—C27 | 120.8 (4) |
O14—C14—O3 | 109.2 (3) | C26—C27—C28 | 119.0 (4) |
O14—C14—C16 | 113.5 (4) | C26—C27—C30 | 120.7 (4) |
O3—C14—C16 | 105.9 (3) | C28—C27—C30 | 120.3 (4) |
O14—C14—C17 | 104.5 (3) | C29—C28—C27 | 120.8 (4) |
O3—C14—C17 | 110.6 (3) | C24—C29—C28 | 119.0 (4) |
Experimental details
Crystal data | |
Chemical formula | C20H30O9S |
Mr | 446.50 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 150 |
a, b, c (Å) | 8.7709 (3), 14.0181 (10), 18.1744 (13) |
V (Å3) | 2234.6 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.25 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9970, 5177, 3591 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.122, 1.09 |
No. of reflections | 5177 |
No. of parameters | 278 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.33 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.00 (12) |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft,1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLUTON92 (Spek, 1992) and PLATON92 (Spek, 1992), SHELXL97.
Bimolecular nucleophilic (SN2) displacements on α-hexopyranoside 2-sulfonates are notoriously difficult to effect with charged nucleophiles (Richardson, 1969). Elimination reactions tend to be favoured with α-mannopyranoside 2-sulfonates (Binkley & Binkley, 1997) and are sometimes accompanied by more deep-seated rearrangements (Vos et al., 1984; Barnes et al., 1996). We reasoned that SN2 displacements on a bicyclic 2-sulfonate, such as (II), stood a much better chance of success since the incipient 2,3-double bond at the ring junction would introduce appreciable torsional strain in the transition state of the competing E2 reaction. The butane-3,4-diacetal, (I), is accessible through the seminal work of Ley's group (Hense et al.,1997; Ley et al., 1997) and is readily transformed into the 2-sulfonates (II) and (III). Sulfonate (II), an oil, reacted readily with sodium azide in dimethylformamide at 343 K to give, principally, the azide (IV). An extremely labile (minor) product of this reaction was identified as the 2,3-unsaturated sugar, (V), by 1H NMR spectroscopy. (III) and (IV) are crystalline. The structure of (III) is reported here; that of (IV) is given in the following paper (Barnes et al., 2002).
(III) did not react with sodium azide in DMF even at 423 K. The p-toluenesulfonate group at C2 would be much less reactive than the SO2CF3 group in (II). In addition, there will be some stabilization of (III) from the close approach of the methyl proton H16c to the centroid of the phenyl ring (3.237 Å). The presence of the sulfonate group made it possible to determine the absolute conformation of (III) by Flack's method (Flack, 1983). Fig. 1 shows that, as expected, (III) retains the conformation of (I). The same is presumably true of (II). Comparison with the structure of (IV) (Barnes et al., 2002) shows that in (IV) the original conformation is preserved at all centers except for inversion of the configuration at the reaction centre C2. Thus the hoped for SN2 displacement had occurred. In (III), the torsion angle O2—C2—C3—H3 is 172.6(?)°, only slightly displaced from the ideal antiperiplanar arrangement favoured by E2 eliminations (Eliel & Wilen, 1994). In (IV), the torsion angles N11—C2—C3—H3 are 61.02(?) and 62.64(?)°, showing the change in configuration at C2. There are no unusual bond lengths or angles in either structure. [Please provide s.u. values for the three torsion angles above]