The X-ray study of the title compound, C23H26O8, (I), confirmed the endo,exo-furofuranone structure of the important intermediate compound in the process of the total synthesis of (±)-epimagnolin A, which employs a new approach involving a highly diastereoselective C-H insertion reaction [Brown et al. (2001). Tetrahedron Lett. 42, 473-475].
Supporting information
CCDC reference: 170299
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.014 Å
- R factor = 0.086
- wR factor = 0.334
- Data-to-parameter ratio = 10.7
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level A:
TYPE_048 Alert A _exptl_absorpt_correction_T_max is not of type numb.
RINTA_01 Alert A The value of Rint is greater than 0.20
Rint given 0.361
| Author response: The crystal was of poor quality and only diffracted weakly
|
Alert Level B:
THETM_01 Alert B The value of sine(theta_max)/wavelength is less than 0.575
Calculated sin(theta_max)/wavelength = 0.5543
| Author response: The crystal was only weakly diffracting
|
PLAT_213 Alert B Atom O2 has ADP max/min Ratio ........... 4.70
| Author response: The -OMe groups are thermally disordered - an attempt to model
this
did not improve the refinement.
|
Alert Level C:
RFACR_01 Alert C The value of the weighted R factor is > 0.25
Weighted R factor given 0.334
PLAT_213 Alert C Atom C3 has ADP max/min Ratio ........... 3.90
2 Alert Level A = Potentially serious problem
2 Alert Level B = Potential problem
2 Alert Level C = Please check
Data collection: COLLECT (Hooft, 1998); cell refinement: SCALEPACK (Otwinoski & Minor, 1997) and COLLECT; data reduction: DENZO (Otwinoski & Minor, 1997), COLLECT and maXus (Mackay et al., 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1993); software used to prepare material for publication: WinGX (Farrugia, 1998).
(1
S*,4
S*,5
R*,8
R*)-8-(3,4-Dimethoxyphenyl)-4-(3,4,5-trimethoxyphenyl)-3,7- dioxabicyclo[3.3.0]octan-2-one
top
Crystal data top
C23H26O8 | F(000) = 912 |
Mr = 430.44 | Dx = 1.318 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.839 (2) Å | Cell parameters from 2999 reflections |
b = 8.0773 (10) Å | θ = 3.0–23.2° |
c = 22.695 (4) Å | µ = 0.10 mm−1 |
β = 91.84 (3)° | T = 150 K |
V = 2169.1 (6) Å3 | Block, colourless |
Z = 4 | 0.10 × 0.10 × 0.10 mm |
Data collection top
Nonius Kappa CCD area-detector diffractometer | 2999 independent reflections |
Radiation source: Nonius FR591 rotating anode | 947 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.361 |
Detector resolution: 9.091 pixels/mm pixels mm-1 | θmax = 23.2°, θmin = 3.0° |
φ and ω scans to fill Ewald sphere | h = −13→13 |
Absorption correction: empirical (using intensity measurements) (SORTAV; Blessing, 1997) | k = −8→8 |
Tmin = 0.990, Tmax = 0.990 (?) | l = −25→25 |
13956 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.086 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.334 | H-atom parameters constrained |
S = 0.81 | w = 1/[σ2(Fo2) + (0.1905P)2] where P = (Fo2 + 2Fc2)/3 |
2999 reflections | (Δ/σ)max = 0.010 |
281 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.0859 (9) | 0.3696 (13) | 0.0602 (5) | 0.079 (3) | |
H1A | 0.0236 | 0.3293 | 0.0346 | 0.118* | |
H1B | 0.0581 | 0.3916 | 0.0997 | 0.118* | |
H1C | 0.1456 | 0.2857 | 0.0628 | 0.118* | |
C2 | 0.1774 (15) | 0.910 (2) | −0.0272 (10) | 0.199 (11) | |
H2A | 0.1214 | 0.8795 | −0.0581 | 0.298* | |
H2B | 0.2470 | 0.9464 | −0.0454 | 0.298* | |
H2C | 0.1474 | 0.9993 | −0.0032 | 0.298* | |
C3 | 0.4607 (14) | 1.0700 (16) | 0.0764 (6) | 0.150 (7) | |
H3A | 0.4704 | 1.1750 | 0.0555 | 0.225* | |
H3B | 0.5283 | 1.0015 | 0.0723 | 0.225* | |
H3C | 0.4493 | 1.0922 | 0.1183 | 0.225* | |
C4 | 0.2729 (7) | 0.5250 (12) | 0.1148 (4) | 0.050 (3) | |
H4 | 0.2509 | 0.4188 | 0.1283 | 0.060* | |
C5 | 0.2191 (8) | 0.5965 (13) | 0.0668 (4) | 0.056 (3) | |
C6 | 0.2495 (11) | 0.7514 (15) | 0.0457 (5) | 0.091 (4) | |
C7 | 0.3373 (11) | 0.8360 (15) | 0.0754 (5) | 0.078 (4) | |
C8 | 0.3924 (8) | 0.7692 (13) | 0.1245 (5) | 0.057 (3) | |
H8 | 0.4506 | 0.8288 | 0.1450 | 0.068* | |
C9 | 0.3603 (7) | 0.6112 (12) | 0.1432 (4) | 0.049 (3) | |
C10 | 0.4171 (7) | 0.5431 (11) | 0.2002 (4) | 0.052 (3) | |
H10 | 0.4869 | 0.6079 | 0.2106 | 0.062* | |
C11 | 0.4271 (7) | 0.2760 (14) | 0.2384 (5) | 0.049 (3) | |
C12 | 0.3704 (7) | 0.3793 (12) | 0.2854 (4) | 0.051 (3) | |
H12 | 0.3021 | 0.3219 | 0.3002 | 0.061* | |
C13 | 0.4501 (8) | 0.4393 (14) | 0.3378 (5) | 0.059 (3) | |
H13 | 0.4069 | 0.4328 | 0.3749 | 0.071* | |
C14 | 0.3720 (8) | 0.6745 (13) | 0.2974 (4) | 0.068 (3) | |
H14A | 0.3877 | 0.7803 | 0.2771 | 0.082* | |
H14B | 0.3118 | 0.6928 | 0.3260 | 0.082* | |
C15 | 0.3380 (7) | 0.5391 (13) | 0.2529 (4) | 0.054 (3) | |
H15 | 0.2562 | 0.5435 | 0.2406 | 0.065* | |
C16 | 0.5580 (8) | 0.3500 (12) | 0.3478 (4) | 0.050 (3) | |
C17 | 0.5734 (9) | 0.2389 (13) | 0.3942 (4) | 0.061 (3) | |
H17 | 0.5131 | 0.2218 | 0.4202 | 0.073* | |
C18 | 0.6743 (8) | 0.1513 (12) | 0.4042 (5) | 0.055 (3) | |
H18 | 0.6819 | 0.0751 | 0.4360 | 0.066* | |
C19 | 0.7611 (7) | 0.1771 (12) | 0.3676 (5) | 0.054 (3) | |
C20 | 0.7496 (8) | 0.2892 (13) | 0.3197 (4) | 0.053 (3) | |
C21 | 0.6506 (8) | 0.3757 (12) | 0.3113 (4) | 0.053 (3) | |
H21 | 0.6443 | 0.4543 | 0.2802 | 0.063* | |
C22 | 0.8290 (8) | 0.3968 (13) | 0.2333 (5) | 0.078 (4) | |
H22A | 0.8984 | 0.3933 | 0.2110 | 0.117* | |
H22B | 0.8140 | 0.5111 | 0.2453 | 0.117* | |
H22C | 0.7656 | 0.3560 | 0.2086 | 0.117* | |
C23 | 0.8817 (9) | 0.0014 (17) | 0.4252 (6) | 0.120 (6) | |
H23A | 0.9574 | −0.0475 | 0.4248 | 0.180* | |
H23B | 0.8251 | −0.0869 | 0.4264 | 0.180* | |
H23C | 0.8755 | 0.0721 | 0.4601 | 0.180* | |
O1 | 0.1307 (6) | 0.5206 (9) | 0.0360 (3) | 0.067 (2) | |
O2 | 0.1940 (14) | 0.8101 (16) | −0.0014 (5) | 0.225 (9) | |
O3 | 0.3652 (9) | 0.9851 (11) | 0.0520 (3) | 0.134 (4) | |
O4 | 0.4454 (4) | 0.3710 (9) | 0.1900 (3) | 0.0537 (19) | |
O5 | 0.4442 (5) | 0.1297 (9) | 0.2388 (3) | 0.0561 (19) | |
O6 | 0.4720 (5) | 0.6101 (9) | 0.3259 (3) | 0.065 (2) | |
O7 | 0.8423 (5) | 0.2937 (8) | 0.2851 (3) | 0.063 (2) | |
O8 | 0.8626 (5) | 0.0989 (8) | 0.3730 (3) | 0.075 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.095 (8) | 0.066 (8) | 0.073 (8) | −0.011 (7) | −0.028 (6) | 0.013 (7) |
C2 | 0.158 (15) | 0.17 (2) | 0.26 (3) | −0.060 (14) | −0.099 (15) | 0.144 (18) |
C3 | 0.236 (17) | 0.118 (13) | 0.095 (11) | −0.144 (13) | 0.001 (11) | 0.001 (9) |
C4 | 0.051 (6) | 0.047 (6) | 0.053 (7) | −0.008 (5) | 0.011 (5) | −0.009 (6) |
C5 | 0.071 (7) | 0.057 (8) | 0.040 (7) | −0.018 (6) | −0.007 (6) | 0.005 (6) |
C6 | 0.153 (12) | 0.073 (9) | 0.043 (8) | −0.055 (9) | −0.025 (8) | 0.025 (7) |
C7 | 0.131 (11) | 0.067 (9) | 0.037 (7) | −0.023 (8) | 0.000 (7) | 0.017 (7) |
C8 | 0.053 (6) | 0.051 (7) | 0.068 (8) | −0.018 (5) | 0.019 (6) | −0.014 (6) |
C9 | 0.038 (6) | 0.049 (7) | 0.059 (7) | −0.003 (5) | 0.006 (5) | −0.011 (6) |
C10 | 0.043 (6) | 0.030 (6) | 0.083 (8) | −0.002 (5) | −0.003 (6) | −0.022 (5) |
C11 | 0.033 (6) | 0.046 (7) | 0.068 (8) | −0.009 (5) | −0.009 (5) | −0.003 (7) |
C12 | 0.043 (6) | 0.055 (7) | 0.055 (7) | 0.003 (5) | 0.004 (5) | −0.007 (6) |
C13 | 0.043 (6) | 0.073 (9) | 0.061 (8) | −0.002 (6) | −0.008 (5) | −0.007 (6) |
C14 | 0.067 (7) | 0.079 (9) | 0.058 (7) | 0.031 (6) | −0.013 (6) | −0.015 (6) |
C15 | 0.042 (6) | 0.068 (8) | 0.051 (7) | 0.007 (5) | 0.007 (5) | −0.019 (6) |
C16 | 0.046 (6) | 0.057 (7) | 0.046 (7) | −0.001 (6) | −0.008 (5) | −0.014 (6) |
C17 | 0.063 (7) | 0.073 (8) | 0.047 (7) | 0.005 (6) | 0.008 (5) | −0.014 (6) |
C18 | 0.042 (6) | 0.055 (7) | 0.069 (8) | 0.002 (6) | −0.001 (5) | −0.002 (6) |
C19 | 0.030 (6) | 0.044 (7) | 0.088 (9) | 0.012 (5) | 0.006 (6) | 0.003 (6) |
C20 | 0.046 (6) | 0.062 (7) | 0.053 (7) | −0.007 (6) | 0.004 (5) | 0.002 (6) |
C21 | 0.047 (6) | 0.042 (6) | 0.069 (8) | 0.000 (6) | −0.017 (6) | −0.014 (6) |
C22 | 0.056 (7) | 0.079 (9) | 0.101 (10) | 0.002 (6) | 0.012 (6) | 0.044 (7) |
C23 | 0.069 (8) | 0.165 (14) | 0.129 (12) | 0.052 (8) | 0.037 (8) | 0.107 (11) |
O1 | 0.097 (5) | 0.066 (5) | 0.038 (4) | −0.021 (4) | −0.019 (4) | 0.008 (4) |
O2 | 0.40 (2) | 0.159 (12) | 0.105 (9) | −0.165 (13) | −0.153 (11) | 0.099 (9) |
O3 | 0.239 (11) | 0.102 (7) | 0.060 (6) | −0.090 (8) | −0.023 (6) | 0.029 (5) |
O4 | 0.046 (4) | 0.062 (5) | 0.054 (5) | 0.001 (3) | 0.007 (3) | −0.012 (4) |
O5 | 0.054 (4) | 0.049 (5) | 0.066 (5) | −0.003 (4) | −0.003 (3) | −0.007 (4) |
O6 | 0.051 (4) | 0.079 (6) | 0.064 (5) | 0.013 (4) | −0.018 (3) | −0.026 (4) |
O7 | 0.040 (4) | 0.063 (5) | 0.088 (6) | 0.006 (3) | 0.005 (4) | 0.031 (4) |
O8 | 0.043 (4) | 0.085 (6) | 0.099 (6) | 0.015 (4) | 0.022 (4) | 0.043 (5) |
Geometric parameters (Å, º) top
C1—O1 | 1.446 (11) | C11—C12 | 1.526 (13) |
C2—O2 | 1.010 (14) | C12—C15 | 1.530 (13) |
C3—O3 | 1.420 (13) | C12—C13 | 1.571 (12) |
C4—C5 | 1.372 (12) | C13—O6 | 1.431 (10) |
C4—C9 | 1.388 (12) | C13—C16 | 1.478 (12) |
C5—O1 | 1.383 (10) | C14—O6 | 1.430 (10) |
C5—C6 | 1.391 (13) | C14—C15 | 1.534 (12) |
C6—O2 | 1.325 (14) | C16—C17 | 1.392 (12) |
C6—C7 | 1.399 (14) | C16—C21 | 1.410 (12) |
C7—O3 | 1.360 (12) | C17—C18 | 1.401 (12) |
C7—C8 | 1.383 (13) | C18—C19 | 1.358 (12) |
C8—C9 | 1.401 (12) | C19—O8 | 1.360 (10) |
C9—C10 | 1.540 (13) | C19—C20 | 1.417 (12) |
C10—O4 | 1.450 (10) | C20—O7 | 1.371 (10) |
C10—C15 | 1.542 (13) | C20—C21 | 1.373 (12) |
C11—O5 | 1.199 (10) | C22—O7 | 1.446 (10) |
C11—O4 | 1.363 (11) | C23—O8 | 1.434 (11) |
| | | |
C5—C4—C9 | 118.6 (10) | C16—C13—C12 | 117.4 (9) |
C4—C5—O1 | 122.7 (9) | O6—C14—C15 | 103.6 (7) |
C4—C5—C6 | 122.2 (10) | C12—C15—C14 | 103.2 (8) |
O1—C5—C6 | 115.2 (9) | C12—C15—C10 | 104.0 (7) |
O2—C6—C5 | 118.2 (11) | C14—C15—C10 | 110.0 (8) |
O2—C6—C7 | 123.7 (11) | C17—C16—C21 | 117.0 (9) |
C5—C6—C7 | 118.1 (11) | C17—C16—C13 | 121.5 (9) |
O3—C7—C8 | 123.1 (11) | C21—C16—C13 | 121.5 (10) |
O3—C7—C6 | 115.5 (11) | C16—C17—C18 | 122.5 (10) |
C8—C7—C6 | 121.4 (11) | C19—C18—C17 | 118.8 (10) |
C7—C8—C9 | 118.3 (10) | C18—C19—O8 | 123.8 (10) |
C4—C9—C8 | 121.4 (10) | C18—C19—C20 | 120.7 (9) |
C4—C9—C10 | 120.7 (9) | O8—C19—C20 | 115.4 (9) |
C8—C9—C10 | 117.7 (9) | O7—C20—C21 | 127.1 (10) |
O4—C10—C9 | 107.7 (8) | O7—C20—C19 | 113.4 (9) |
O4—C10—C15 | 104.7 (7) | C21—C20—C19 | 119.5 (9) |
C9—C10—C15 | 113.4 (8) | C20—C21—C16 | 121.3 (10) |
O5—C11—O4 | 122.0 (10) | C5—O1—C1 | 117.6 (7) |
O5—C11—C12 | 127.7 (10) | C2—O2—C6 | 146.7 (17) |
O4—C11—C12 | 109.9 (9) | C7—O3—C3 | 118.4 (10) |
C11—C12—C15 | 103.5 (8) | C11—O4—C10 | 111.5 (8) |
C11—C12—C13 | 115.5 (7) | C14—O6—C13 | 106.5 (8) |
C15—C12—C13 | 103.9 (8) | C20—O7—C22 | 114.4 (7) |
O6—C13—C16 | 109.8 (8) | C19—O8—C23 | 116.4 (8) |
O6—C13—C12 | 105.2 (8) | | |