Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800018092/ob6002sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800018092/ob60021sup2.hkl |
CCDC reference: 155875
Trimethylsilyl trifluoromethanesulfonate (51 ml, 0.266 mmol) and silver perchlorate (2 mg, 5 mol%) were added to a stirred solution of 3-bromo-1,4-dimethoxy-5-hydroxynaphthalene (4) (50 mg, 0.177 mmol) and tri-O-benzyl-2-deoxy-D-glucosyl acetate (5) (101 mg, 210 mmol) in dry acetonitrile (5 ml) at 0 °C. The mixture was stirred for 1 h then quenched with aqueous bicarbonate solution (5 ml). The reaction mixture was extracted with dichloromethane (3 x 50 ml), washed with water (100 ml) and dried (magnesium sulfate). The solvent was removed at reduced pressure and the oily residue purified by flash chromatography using hexane-ethyl acetate (4:1) as eluent to give a mixture of a rearranged C-glycoside and b-C-glycoside (6) (71 mg, 6:1). This mixture of glycosides was subjected to HPLC.
Triethylamine (0.50 ml, 3.59 mmol), acetic anhydride (0.25 ml, 2.65 mmol) and a catalytic quantity of dimethylaminopyridine were added to a solution of the above rearranged C-glycoside (98 mg, 0.166 mmol) in dichloromethane (2 ml). The solution was stirred overnight then the solvent removed at reduced pressure. The residue was purified by flash chromatography using hexane-ethyl acetate (4:1) to give the acetate (1) (99 mg, 94%) which was recrystallized from hexane-ethyl acetate to give pale brown needles m.p. 477–478 K.
Data collection: MSC AFC Diffractometer Control (MSC, 1995); cell refinement: MSC AFC Diffractometer Control (MSC, 1995); data reduction: TEXSAN (MSC, 1992); program(s) used to solve structure: SIR92 (Altomare, et al. 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN for Windows (MSC, 1997).
Fig. 1. ORTEP (Johnson, 1976, Hall et al. 1999) projection of (1) with displacement ellipsoids shown at the 20% level. |
C34H33BrO7 | Dx = 1.393 Mg m−3 |
Mr = 633.51 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, P212121 | Cell parameters from 25 reflections |
a = 19.515 (1) Å | θ = 26.6–30.2° |
b = 23.667 (2) Å | µ = 2.25 mm−1 |
c = 6.541 (2) Å | T = 294 K |
V = 3021.0 (10) Å3 | Acicular, pale brown |
Z = 4 | 0.55 × 0.13 × 0.08 mm |
F(000) = 1312 |
Rigaku AFC7R diffractometer | 2068 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.000 |
Graphite monochromator | θmax = 65.0°, θmin = 2.9° |
ω–2θ scans | h = 0→22 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→27 |
Tmin = 0.715, Tmax = 0.835 | l = 0→7 |
2962 measured reflections | 3 standard reflections every 150 reflections |
2962 independent reflections | intensity decay: 2.4% |
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)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0579P)2 + 0.6329P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
2962 reflections | Δρmax = 0.31 e Å−3 |
382 parameters | Δρmin = −0.34 e Å−3 |
0 restraints | Absolute structure: Flack (1983) and Bernardinelli & Flack(1985); No Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.06 (3) |
C34H33BrO7 | V = 3021.0 (10) Å3 |
Mr = 633.51 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 19.515 (1) Å | µ = 2.25 mm−1 |
b = 23.667 (2) Å | T = 294 K |
c = 6.541 (2) Å | 0.55 × 0.13 × 0.08 mm |
Rigaku AFC7R diffractometer | 2068 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.000 |
Tmin = 0.715, Tmax = 0.835 | 3 standard reflections every 150 reflections |
2962 measured reflections | intensity decay: 2.4% |
2962 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.114 | Δρmax = 0.31 e Å−3 |
S = 1.02 | Δρmin = −0.34 e Å−3 |
2962 reflections | Absolute structure: Flack (1983) and Bernardinelli & Flack(1985); No Friedel pairs |
382 parameters | Absolute structure parameter: −0.06 (3) |
0 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 | ||
Br1 | 0.96750 (3) | 0.09686 (3) | −0.05259 (13) | 0.0935 (3) | |
O1 | 0.56407 (16) | 0.20795 (14) | 0.4274 (6) | 0.0644 (9) | |
O2 | 0.56036 (17) | 0.34224 (14) | 0.5699 (7) | 0.0745 (11) | |
O3 | 0.54484 (19) | 0.18553 (15) | 0.8661 (7) | 0.0843 (12) | |
O4 | 0.74688 (16) | 0.23284 (14) | 0.1453 (5) | 0.0595 (8) | |
O5 | 0.8305 (2) | 0.26370 (16) | 0.3496 (7) | 0.0776 (11) | |
O6 | 0.85879 (17) | 0.18547 (15) | −0.0133 (6) | 0.0659 (9) | |
O7 | 0.8080 (2) | 0.00178 (14) | 0.4892 (8) | 0.0842 (13) | |
C1 | 0.6316 (2) | 0.2297 (2) | 0.3920 (8) | 0.0556 (11) | |
H1 | 0.6318 | 0.2493 | 0.2600 | 0.067* | |
C2 | 0.6533 (2) | 0.27178 (17) | 0.5577 (8) | 0.0519 (11) | |
H2 | 0.7035 | 0.2722 | 0.5597 | 0.062* | |
C3 | 0.6298 (2) | 0.25151 (19) | 0.7669 (8) | 0.0572 (12) | |
H3A | 0.6540 | 0.2170 | 0.8015 | 0.069* | |
H3B | 0.6414 | 0.2798 | 0.8685 | 0.069* | |
C4 | 0.5532 (3) | 0.2405 (2) | 0.7740 (9) | 0.0620 (13) | |
H4 | 0.5311 | 0.2690 | 0.8600 | 0.074* | |
C5 | 0.5235 (2) | 0.2429 (2) | 0.5625 (9) | 0.0629 (13) | |
H5 | 0.4779 | 0.2256 | 0.5699 | 0.075* | |
C6 | 0.5133 (3) | 0.3027 (2) | 0.4865 (11) | 0.0785 (17) | |
H6A | 0.5176 | 0.3030 | 0.3388 | 0.094* | |
H6B | 0.4671 | 0.3147 | 0.5199 | 0.094* | |
C7 | 0.6295 (2) | 0.33348 (18) | 0.5157 (10) | 0.0654 (14) | |
H7 | 0.6347 | 0.3412 | 0.3693 | 0.078* | |
C8 | 0.6720 (3) | 0.37487 (19) | 0.6311 (11) | 0.0693 (15) | |
C9 | 0.6497 (3) | 0.3983 (2) | 0.8139 (12) | 0.0847 (19) | |
H9 | 0.6066 | 0.3891 | 0.8641 | 0.102* | |
C10 | 0.6916 (4) | 0.4357 (2) | 0.9235 (15) | 0.102 (2) | |
H10 | 0.6758 | 0.4519 | 1.0442 | 0.123* | |
C11 | 0.7563 (4) | 0.4484 (3) | 0.8520 (17) | 0.108 (3) | |
H11 | 0.7848 | 0.4725 | 0.9256 | 0.130* | |
C12 | 0.7783 (4) | 0.4252 (3) | 0.6719 (17) | 0.101 (2) | |
H12 | 0.8218 | 0.4337 | 0.6229 | 0.122* | |
C13 | 0.7367 (3) | 0.3898 (2) | 0.5638 (13) | 0.0831 (18) | |
H13 | 0.7524 | 0.3751 | 0.4405 | 0.100* | |
C14 | 0.6804 (2) | 0.17996 (18) | 0.3789 (8) | 0.0535 (11) | |
C15 | 0.6690 (3) | 0.13042 (19) | 0.4902 (9) | 0.0621 (13) | |
H15 | 0.6289 | 0.1266 | 0.5658 | 0.075* | |
C16 | 0.7157 (3) | 0.08766 (19) | 0.4899 (10) | 0.0668 (14) | |
H16 | 0.7082 | 0.0560 | 0.5709 | 0.080* | |
C17 | 0.7755 (2) | 0.09084 (19) | 0.3677 (8) | 0.0583 (12) | |
C18 | 0.8241 (3) | 0.04559 (19) | 0.3654 (10) | 0.0656 (13) | |
C19 | 0.8813 (3) | 0.0487 (2) | 0.2487 (11) | 0.0741 (15) | |
H19 | 0.9139 | 0.0200 | 0.2524 | 0.089* | |
C20 | 0.8904 (2) | 0.0960 (2) | 0.1220 (8) | 0.0632 (12) | |
C21 | 0.8461 (2) | 0.1404 (2) | 0.1148 (8) | 0.0555 (11) | |
C22 | 0.7869 (2) | 0.13918 (18) | 0.2459 (8) | 0.0502 (11) | |
C23 | 0.7386 (2) | 0.18412 (19) | 0.2630 (8) | 0.0532 (11) | |
C24 | 0.7972 (3) | 0.2688 (2) | 0.1991 (10) | 0.0674 (14) | |
C25 | 0.8021 (3) | 0.3149 (3) | 0.0407 (14) | 0.104 (3) | |
H25A | 0.8277 | 0.3461 | 0.0953 | 0.156* | |
H25B | 0.7569 | 0.3275 | 0.0047 | 0.156* | |
H25C | 0.8248 | 0.3006 | −0.0788 | 0.156* | |
C26 | 0.8297 (3) | 0.1785 (4) | −0.2147 (9) | 0.103 (2) | |
H26A | 0.8441 | 0.1430 | −0.2708 | 0.154* | |
H26B | 0.8450 | 0.2086 | −0.3017 | 0.154* | |
H26C | 0.7806 | 0.1793 | −0.2054 | 0.154* | |
C27 | 0.8576 (3) | −0.0429 (2) | 0.5058 (13) | 0.096 (2) | |
H27A | 0.8668 | −0.0581 | 0.3725 | 0.144* | |
H27B | 0.8399 | −0.0722 | 0.5925 | 0.144* | |
H27C | 0.8992 | −0.0283 | 0.5633 | 0.144* | |
C28 | 0.4846 (3) | 0.1790 (2) | 0.9722 (12) | 0.0849 (18) | |
H28A | 0.4470 | 0.1951 | 0.8947 | 0.102* | |
H28B | 0.4875 | 0.1986 | 1.1022 | 0.102* | |
C29 | 0.4722 (3) | 0.1169 (2) | 1.0074 (9) | 0.0675 (14) | |
C30 | 0.4775 (3) | 0.0943 (3) | 1.2008 (10) | 0.0789 (16) | |
H30 | 0.4909 | 0.1173 | 1.3092 | 0.095* | |
C31 | 0.4632 (4) | 0.0379 (3) | 1.2355 (12) | 0.0911 (19) | |
H31 | 0.4657 | 0.0231 | 1.3670 | 0.109* | |
C32 | 0.4453 (3) | 0.0042 (3) | 1.0755 (15) | 0.094 (2) | |
H32 | 0.4352 | −0.0336 | 1.0984 | 0.113* | |
C33 | 0.4421 (4) | 0.0251 (3) | 0.8851 (14) | 0.097 (2) | |
H33 | 0.4302 | 0.0014 | 0.7772 | 0.116* | |
C34 | 0.4565 (4) | 0.0818 (3) | 0.8475 (11) | 0.0880 (19) | |
H34 | 0.4553 | 0.0958 | 0.7147 | 0.106* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0722 (4) | 0.0954 (4) | 0.1128 (5) | 0.0176 (3) | 0.0302 (4) | 0.0167 (4) |
O1 | 0.0494 (17) | 0.069 (2) | 0.075 (2) | −0.0040 (15) | 0.0021 (18) | −0.0120 (19) |
O2 | 0.0603 (19) | 0.0546 (18) | 0.109 (3) | 0.0108 (15) | −0.015 (2) | 0.007 (2) |
O3 | 0.075 (2) | 0.062 (2) | 0.116 (3) | 0.0093 (18) | 0.031 (2) | 0.020 (2) |
O4 | 0.0522 (17) | 0.0634 (18) | 0.063 (2) | 0.0027 (15) | −0.0038 (17) | 0.0188 (18) |
O5 | 0.074 (2) | 0.067 (2) | 0.092 (3) | −0.0155 (19) | −0.013 (2) | 0.007 (2) |
O6 | 0.0595 (19) | 0.078 (2) | 0.060 (2) | 0.0061 (16) | 0.0033 (17) | 0.0157 (19) |
O7 | 0.082 (2) | 0.0570 (19) | 0.114 (4) | 0.0130 (17) | 0.022 (3) | 0.023 (2) |
C1 | 0.055 (2) | 0.057 (3) | 0.055 (3) | 0.001 (2) | −0.001 (2) | 0.006 (2) |
C2 | 0.048 (2) | 0.046 (2) | 0.061 (3) | 0.0033 (18) | −0.003 (2) | 0.005 (2) |
C3 | 0.064 (3) | 0.044 (2) | 0.063 (3) | 0.003 (2) | −0.005 (3) | 0.003 (2) |
C4 | 0.068 (3) | 0.049 (2) | 0.069 (3) | 0.005 (2) | 0.014 (3) | 0.007 (3) |
C5 | 0.044 (2) | 0.067 (3) | 0.078 (3) | −0.001 (2) | −0.002 (3) | 0.000 (3) |
C6 | 0.063 (3) | 0.072 (3) | 0.101 (5) | 0.006 (2) | −0.017 (3) | 0.009 (4) |
C7 | 0.065 (3) | 0.047 (2) | 0.084 (4) | −0.002 (2) | −0.006 (3) | 0.012 (3) |
C8 | 0.073 (3) | 0.040 (2) | 0.096 (4) | 0.005 (2) | −0.010 (3) | 0.012 (3) |
C9 | 0.080 (4) | 0.053 (3) | 0.121 (6) | 0.009 (3) | −0.007 (4) | −0.010 (4) |
C10 | 0.113 (5) | 0.057 (3) | 0.137 (7) | 0.015 (3) | −0.012 (5) | −0.022 (4) |
C11 | 0.098 (5) | 0.050 (3) | 0.175 (9) | −0.006 (3) | −0.033 (6) | 0.007 (5) |
C12 | 0.089 (4) | 0.058 (3) | 0.157 (8) | −0.009 (3) | 0.000 (5) | 0.013 (5) |
C13 | 0.087 (4) | 0.050 (3) | 0.112 (5) | −0.014 (3) | 0.008 (4) | 0.012 (4) |
C14 | 0.054 (2) | 0.049 (2) | 0.057 (3) | −0.004 (2) | −0.001 (2) | −0.002 (2) |
C15 | 0.063 (3) | 0.056 (3) | 0.068 (3) | −0.004 (2) | 0.009 (3) | 0.003 (3) |
C16 | 0.071 (3) | 0.049 (2) | 0.081 (4) | −0.004 (2) | 0.010 (3) | 0.006 (3) |
C17 | 0.059 (2) | 0.048 (2) | 0.068 (3) | −0.003 (2) | −0.003 (2) | −0.002 (3) |
C18 | 0.066 (3) | 0.049 (3) | 0.082 (4) | −0.001 (2) | 0.001 (3) | 0.006 (3) |
C19 | 0.064 (3) | 0.069 (3) | 0.090 (4) | 0.013 (3) | 0.002 (3) | 0.010 (3) |
C20 | 0.066 (3) | 0.058 (3) | 0.066 (3) | 0.003 (2) | 0.003 (2) | −0.002 (3) |
C21 | 0.053 (2) | 0.061 (3) | 0.053 (3) | 0.002 (2) | −0.007 (2) | 0.001 (2) |
C22 | 0.048 (2) | 0.047 (2) | 0.055 (3) | −0.0031 (18) | −0.004 (2) | 0.000 (2) |
C23 | 0.054 (2) | 0.056 (2) | 0.050 (3) | −0.003 (2) | −0.011 (2) | 0.005 (2) |
C24 | 0.056 (3) | 0.062 (3) | 0.084 (4) | 0.002 (2) | 0.005 (3) | 0.021 (3) |
C25 | 0.082 (4) | 0.087 (4) | 0.143 (7) | −0.001 (3) | 0.016 (5) | 0.061 (5) |
C26 | 0.092 (5) | 0.165 (7) | 0.052 (3) | 0.030 (5) | −0.005 (3) | 0.013 (4) |
C27 | 0.099 (4) | 0.073 (4) | 0.117 (6) | 0.019 (3) | 0.014 (4) | 0.033 (4) |
C28 | 0.095 (4) | 0.069 (3) | 0.091 (4) | −0.013 (3) | 0.024 (4) | 0.002 (3) |
C29 | 0.069 (3) | 0.062 (3) | 0.072 (4) | −0.011 (2) | 0.015 (3) | −0.005 (3) |
C30 | 0.090 (4) | 0.071 (3) | 0.076 (4) | 0.001 (3) | 0.013 (3) | −0.005 (3) |
C31 | 0.107 (5) | 0.071 (4) | 0.095 (5) | −0.002 (4) | 0.016 (5) | 0.010 (4) |
C32 | 0.084 (4) | 0.062 (3) | 0.135 (7) | −0.012 (3) | 0.013 (5) | 0.013 (5) |
C33 | 0.100 (5) | 0.074 (4) | 0.117 (6) | −0.020 (3) | −0.004 (4) | −0.019 (4) |
C34 | 0.109 (5) | 0.080 (4) | 0.075 (4) | −0.016 (4) | −0.004 (4) | −0.002 (3) |
Br1—C20 | 1.889 (5) | C12—H12 | 0.9300 |
O1—C1 | 1.434 (5) | C13—H13 | 0.9300 |
O1—C5 | 1.447 (6) | C14—C23 | 1.370 (6) |
O2—C7 | 1.411 (6) | C14—C15 | 1.398 (6) |
O2—C6 | 1.421 (6) | C15—C16 | 1.362 (7) |
O3—C28 | 1.373 (7) | C15—H15 | 0.9300 |
O3—C4 | 1.442 (6) | C16—C17 | 1.416 (7) |
O4—C24 | 1.346 (7) | C16—H16 | 0.9300 |
O4—C23 | 1.396 (5) | C17—C22 | 1.412 (7) |
O5—C24 | 1.187 (7) | C17—C18 | 1.430 (6) |
O6—C21 | 1.380 (6) | C18—C19 | 1.355 (8) |
O6—C26 | 1.444 (7) | C19—C20 | 1.404 (7) |
O7—C18 | 1.352 (6) | C19—H19 | 0.9300 |
O7—C27 | 1.437 (6) | C20—C21 | 1.361 (7) |
C1—C14 | 1.516 (6) | C21—C22 | 1.438 (7) |
C1—C2 | 1.531 (7) | C22—C23 | 1.426 (6) |
C1—H1 | 0.9800 | C24—C25 | 1.508 (8) |
C2—C3 | 1.521 (7) | C25—H25A | 0.9600 |
C2—C7 | 1.557 (6) | C25—H25B | 0.9600 |
C2—H2 | 0.9800 | C25—H25C | 0.9600 |
C3—C4 | 1.519 (7) | C26—H26A | 0.9600 |
C3—H3A | 0.9700 | C26—H26B | 0.9600 |
C3—H3B | 0.9700 | C26—H26C | 0.9600 |
C4—C5 | 1.501 (8) | C27—H27A | 0.9600 |
C4—H4 | 0.9800 | C27—H27B | 0.9600 |
C5—C6 | 1.512 (7) | C27—H27C | 0.9600 |
C5—H5 | 0.9800 | C28—C29 | 1.508 (7) |
C6—H6A | 0.9700 | C28—H28A | 0.9700 |
C6—H6B | 0.9700 | C28—H28B | 0.9700 |
C7—C8 | 1.489 (8) | C29—C34 | 1.370 (8) |
C7—H7 | 0.9800 | C29—C30 | 1.377 (9) |
C8—C13 | 1.383 (8) | C30—C31 | 1.383 (8) |
C8—C9 | 1.388 (9) | C30—H30 | 0.9300 |
C9—C10 | 1.401 (9) | C31—C32 | 1.361 (11) |
C9—H9 | 0.9300 | C31—H31 | 0.9300 |
C10—C11 | 1.381 (10) | C32—C33 | 1.341 (11) |
C10—H10 | 0.9300 | C32—H32 | 0.9300 |
C11—C12 | 1.369 (12) | C33—C34 | 1.393 (9) |
C11—H11 | 0.9300 | C33—H33 | 0.9300 |
C12—C13 | 1.365 (10) | C34—H34 | 0.9300 |
C1—O1—C5 | 113.3 (4) | C14—C15—H15 | 119.5 |
C7—O2—C6 | 115.2 (4) | C15—C16—C17 | 120.9 (5) |
C28—O3—C4 | 114.1 (4) | C15—C16—H16 | 119.6 |
C24—O4—C23 | 117.6 (4) | C17—C16—H16 | 119.6 |
C21—O6—C26 | 113.3 (5) | C22—C17—C16 | 119.4 (4) |
C18—O7—C27 | 117.0 (4) | C22—C17—C18 | 119.8 (4) |
O1—C1—C14 | 107.9 (4) | C16—C17—C18 | 120.8 (5) |
O1—C1—C2 | 111.9 (4) | O7—C18—C19 | 124.7 (5) |
C14—C1—C2 | 111.8 (4) | O7—C18—C17 | 114.5 (5) |
O1—C1—H1 | 108.4 | C19—C18—C17 | 120.8 (5) |
C14—C1—H1 | 108.4 | C18—C19—C20 | 118.7 (5) |
C2—C1—H1 | 108.4 | C18—C19—H19 | 120.7 |
C3—C2—C1 | 110.4 (3) | C20—C19—H19 | 120.7 |
C3—C2—C7 | 111.4 (4) | C21—C20—C19 | 123.7 (5) |
C1—C2—C7 | 113.7 (4) | C21—C20—Br1 | 118.5 (4) |
C3—C2—H2 | 107.0 | C19—C20—Br1 | 117.8 (4) |
C1—C2—H2 | 107.0 | C20—C21—O6 | 120.2 (4) |
C7—C2—H2 | 107.0 | C20—C21—C22 | 118.3 (4) |
C4—C3—C2 | 112.2 (4) | O6—C21—C22 | 121.5 (4) |
C4—C3—H3A | 109.2 | C17—C22—C23 | 117.1 (4) |
C2—C3—H3A | 109.2 | C17—C22—C21 | 118.6 (4) |
C4—C3—H3B | 109.2 | C23—C22—C21 | 124.3 (4) |
C2—C3—H3B | 109.2 | C14—C23—O4 | 117.4 (4) |
H3A—C3—H3B | 107.9 | C14—C23—C22 | 122.6 (4) |
O3—C4—C5 | 112.1 (4) | O4—C23—C22 | 119.8 (4) |
O3—C4—C3 | 106.2 (4) | O5—C24—O4 | 123.5 (5) |
C5—C4—C3 | 110.2 (4) | O5—C24—C25 | 127.5 (6) |
O3—C4—H4 | 109.4 | O4—C24—C25 | 108.9 (5) |
C5—C4—H4 | 109.4 | C24—C25—H25A | 109.5 |
C3—C4—H4 | 109.4 | C24—C25—H25B | 109.5 |
O1—C5—C4 | 109.2 (4) | H25A—C25—H25B | 109.5 |
O1—C5—C6 | 114.0 (5) | C24—C25—H25C | 109.5 |
C4—C5—C6 | 113.0 (5) | H25A—C25—H25C | 109.5 |
O1—C5—H5 | 106.7 | H25B—C25—H25C | 109.5 |
C4—C5—H5 | 106.7 | O6—C26—H26A | 109.5 |
C6—C5—H5 | 106.7 | O6—C26—H26B | 109.5 |
O2—C6—C5 | 113.9 (4) | H26A—C26—H26B | 109.5 |
O2—C6—H6A | 108.8 | O6—C26—H26C | 109.5 |
C5—C6—H6A | 108.8 | H26A—C26—H26C | 109.5 |
O2—C6—H6B | 108.8 | H26B—C26—H26C | 109.5 |
C5—C6—H6B | 108.8 | O7—C27—H27A | 109.5 |
H6A—C6—H6B | 107.7 | O7—C27—H27B | 109.5 |
O2—C7—C8 | 108.0 (5) | H27A—C27—H27B | 109.5 |
O2—C7—C2 | 112.3 (4) | O7—C27—H27C | 109.5 |
C8—C7—C2 | 111.2 (4) | H27A—C27—H27C | 109.5 |
O2—C7—H7 | 108.4 | H27B—C27—H27C | 109.5 |
C8—C7—H7 | 108.4 | O3—C28—C29 | 108.9 (5) |
C2—C7—H7 | 108.4 | O3—C28—H28A | 109.9 |
C13—C8—C9 | 117.2 (6) | C29—C28—H28A | 109.9 |
C13—C8—C7 | 121.0 (6) | O3—C28—H28B | 109.9 |
C9—C8—C7 | 121.7 (5) | C29—C28—H28B | 109.9 |
C8—C9—C10 | 120.8 (7) | H28A—C28—H28B | 108.3 |
C8—C9—H9 | 119.6 | C34—C29—C30 | 118.9 (5) |
C10—C9—H9 | 119.6 | C34—C29—C28 | 120.7 (6) |
C11—C10—C9 | 119.8 (8) | C30—C29—C28 | 120.4 (6) |
C11—C10—H10 | 120.1 | C29—C30—C31 | 120.6 (7) |
C9—C10—H10 | 120.1 | C29—C30—H30 | 119.7 |
C12—C11—C10 | 119.4 (8) | C31—C30—H30 | 119.7 |
C12—C11—H11 | 120.3 | C32—C31—C30 | 119.4 (7) |
C10—C11—H11 | 120.3 | C32—C31—H31 | 120.3 |
C13—C12—C11 | 120.4 (7) | C30—C31—H31 | 120.3 |
C13—C12—H12 | 119.8 | C33—C32—C31 | 120.7 (6) |
C11—C12—H12 | 119.8 | C33—C32—H32 | 119.6 |
C12—C13—C8 | 122.3 (8) | C31—C32—H32 | 119.6 |
C12—C13—H13 | 118.8 | C32—C33—C34 | 120.6 (7) |
C8—C13—H13 | 118.8 | C32—C33—H33 | 119.7 |
C23—C14—C15 | 118.7 (4) | C34—C33—H33 | 119.7 |
C23—C14—C1 | 119.7 (4) | C29—C34—C33 | 119.6 (7) |
C15—C14—C1 | 121.5 (4) | C29—C34—H34 | 120.2 |
C16—C15—C14 | 121.1 (5) | C33—C34—H34 | 120.2 |
C16—C15—H15 | 119.5 | ||
C5—O1—C1—C14 | 143.3 (4) | C27—O7—C18—C19 | 3.8 (9) |
C5—O1—C1—C2 | 20.0 (5) | C27—O7—C18—C17 | −175.1 (6) |
O1—C1—C2—C3 | 40.0 (5) | C22—C17—C18—O7 | 179.5 (5) |
C14—C1—C2—C3 | −81.1 (5) | C16—C17—C18—O7 | −1.0 (8) |
O1—C1—C2—C7 | −86.0 (5) | C22—C17—C18—C19 | 0.5 (8) |
C14—C1—C2—C7 | 152.8 (4) | C16—C17—C18—C19 | −179.9 (6) |
C1—C2—C3—C4 | −55.2 (5) | O7—C18—C19—C20 | 178.0 (5) |
C7—C2—C3—C4 | 72.1 (5) | C17—C18—C19—C20 | −3.2 (9) |
C28—O3—C4—C5 | −89.0 (6) | C18—C19—C20—C21 | 2.5 (9) |
C28—O3—C4—C3 | 150.6 (5) | C18—C19—C20—Br1 | −175.8 (5) |
C2—C3—C4—O3 | 131.5 (4) | C19—C20—C21—O6 | 179.7 (5) |
C2—C3—C4—C5 | 9.8 (6) | Br1—C20—C21—O6 | −1.9 (6) |
C1—O1—C5—C4 | −68.2 (5) | C19—C20—C21—C22 | 0.8 (8) |
C1—O1—C5—C6 | 59.2 (5) | Br1—C20—C21—C22 | 179.1 (3) |
O3—C4—C5—O1 | −68.3 (5) | C26—O6—C21—C20 | 89.6 (6) |
C3—C4—C5—O1 | 49.8 (5) | C26—O6—C21—C22 | −91.4 (5) |
O3—C4—C5—C6 | 163.7 (4) | C16—C17—C22—C23 | 3.7 (7) |
C3—C4—C5—C6 | −78.2 (5) | C18—C17—C22—C23 | −176.8 (5) |
C7—O2—C6—C5 | 64.8 (7) | C16—C17—C22—C21 | −176.8 (5) |
O1—C5—C6—O2 | −96.4 (6) | C18—C17—C22—C21 | 2.8 (7) |
C4—C5—C6—O2 | 29.1 (7) | C20—C21—C22—C17 | −3.4 (7) |
C6—O2—C7—C8 | −174.7 (5) | O6—C21—C22—C17 | 177.7 (4) |
C6—O2—C7—C2 | −51.8 (7) | C20—C21—C22—C23 | 176.1 (5) |
C3—C2—C7—O2 | −45.3 (6) | O6—C21—C22—C23 | −2.8 (7) |
C1—C2—C7—O2 | 80.2 (6) | C15—C14—C23—O4 | 176.8 (4) |
C3—C2—C7—C8 | 75.8 (5) | C1—C14—C23—O4 | −6.1 (7) |
C1—C2—C7—C8 | −158.7 (5) | C15—C14—C23—C22 | 2.2 (7) |
O2—C7—C8—C13 | −158.2 (5) | C1—C14—C23—C22 | 179.3 (4) |
C2—C7—C8—C13 | 78.2 (7) | C24—O4—C23—C14 | 111.8 (5) |
O2—C7—C8—C9 | 24.4 (7) | C24—O4—C23—C22 | −73.5 (6) |
C2—C7—C8—C9 | −99.2 (6) | C17—C22—C23—C14 | −5.1 (7) |
C13—C8—C9—C10 | 0.3 (8) | C21—C22—C23—C14 | 175.4 (4) |
C7—C8—C9—C10 | 177.8 (5) | C17—C22—C23—O4 | −179.5 (4) |
C8—C9—C10—C11 | −1.6 (10) | C21—C22—C23—O4 | 1.0 (7) |
C9—C10—C11—C12 | 1.5 (10) | C23—O4—C24—O5 | −6.5 (8) |
C10—C11—C12—C13 | −0.1 (10) | C23—O4—C24—C25 | 174.1 (4) |
C11—C12—C13—C8 | −1.2 (10) | C4—O3—C28—C29 | 163.7 (5) |
C9—C8—C13—C12 | 1.1 (9) | O3—C28—C29—C34 | −69.1 (8) |
C7—C8—C13—C12 | −176.4 (6) | O3—C28—C29—C30 | 110.0 (7) |
O1—C1—C14—C23 | 151.4 (4) | C34—C29—C30—C31 | −3.8 (10) |
C2—C1—C14—C23 | −85.1 (5) | C28—C29—C30—C31 | 177.0 (6) |
O1—C1—C14—C15 | −31.5 (6) | C29—C30—C31—C32 | 1.7 (11) |
C2—C1—C14—C15 | 91.9 (5) | C30—C31—C32—C33 | 0.6 (11) |
C23—C14—C15—C16 | 2.2 (8) | C31—C32—C33—C34 | −0.5 (12) |
C1—C14—C15—C16 | −174.9 (5) | C30—C29—C34—C33 | 3.8 (10) |
C14—C15—C16—C17 | −3.5 (9) | C28—C29—C34—C33 | −177.0 (6) |
C15—C16—C17—C22 | 0.4 (8) | C32—C33—C34—C29 | −1.7 (12) |
C15—C16—C17—C18 | −179.1 (5) |
Experimental details
Crystal data | |
Chemical formula | C34H33BrO7 |
Mr | 633.51 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 294 |
a, b, c (Å) | 19.515 (1), 23.667 (2), 6.541 (2) |
V (Å3) | 3021.0 (10) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 2.25 |
Crystal size (mm) | 0.55 × 0.13 × 0.08 |
Data collection | |
Diffractometer | Rigaku AFC7R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.715, 0.835 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2962, 2962, 2068 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.588 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.114, 1.02 |
No. of reflections | 2962 |
No. of parameters | 382 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.34 |
Absolute structure | Flack (1983) and Bernardinelli & Flack(1985); No Friedel pairs |
Absolute structure parameter | −0.06 (3) |
Computer programs: MSC AFC Diffractometer Control (MSC, 1995), TEXSAN (MSC, 1992), SIR92 (Altomare, et al. 1993), SHELXL97 (Sheldrick, 1997), TEXSAN for Windows (MSC, 1997).
Recent synthetic effort has been directed towards the synthesis of the pyranonaphthoquinone antibiotic medermycin (2) which was isolated from Streptomyces tanashiensis and contains a C-glycoside linkage to a 2-deoxy sugar (Takano et al., 1976). As part of this programme we embarked on model studies directed towards the synthesis of the 2-deoxyglucosyl analogue of medermycin (3). The key step in the approach to (3) involved the direct C-glycosylation of 3-bromonaphthol (4) with a 2-deoxyglucosyl donor (5) (Brimble and Brenstrum, 2000) (Scheme 1) which was expected to afford the desired C-glycoside (6). Unfortunately this critical C-glycosylation reaction afforded predominantly C-glycoside (1) wherein extensive rearrangement of the 2-deoxyglucosyl moiety had taken place. The structure of this rearranged C-glycoside was established by X-ray crystallography of the acetate derivative of the initial glycosylation product (Fig. 1).
The structure of this rearranged C-glycoside (1) clearly shows that extensive rearrangement of the carbohydrate skeleton has taken place. This rearrangement has been proposed to occur via an unusual 1,6-hydride shift similar to that observed by Steel et al. in the dimerization of tri-O-benzyl-D-glucal (Byerley et al.,1998). The X-ray structure also clearly establishes that the naphthalene ring is endo to the bicylic ring system