Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801012508/cv6045sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801012508/cv6045Isup2.hkl |
CCDC reference: 170936
To a solution of 3-furoic acid (76 mg, 0.68 mmol) in dry methylene chloride (2.5 ml) and dry DMF (5 µl), oxalyl chloride (120 µl, 1.36 mmol) was added. The solution was refluxed overnight, then cooled and the solvent removed in vacuo. After redisolving the residue in dry methylene chloride (2.5 ml), a solution of trans-2-(1-naphthyl)cyclohexanol (136 mg, 0.9 equivalents) in dry methylene chloride (2 ml) was added followed by dry triethylamine (189 µl) and DMAP (9 mg). The reaction was stirred at room temperature for 36 h. After adding Et2O (25 ml), the solution was washed with 5% HCl (10 ml) and water (20 ml), dried over MgSO4, then filtered and evaporated in vacuo to give the crude product as an oil. Purification via a short column (silica gel, EtOAc) followed by radial chromatography (EtOAc hexanes, 20:1 to 5:1), gave recovered trans-2-(1-naphthyl)cyclohexanol (41 mg) and the title product (I) (135 mg) as a white crsytalline solid (m.p. 370 K).
The space group, P21/c, was uniquely determined from the systematic absences. Most of the H atoms were located from difference maps. The H atoms were included at geometrically idealized positions with C–H = 0.93–0.98 Å, in a riding mode with isotropic displacement parameters 1.2 times the displacement parameters of the atoms to which they were attached.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1994); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN; software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Fig. 1. ORTEPII (Johnson, 1976) drawing of (I). Displacement ellipsoids have been plotted at the 30% probability level. |
C21H20O3 | F(000) = 680 |
Mr = 320.37 | Dx = 1.238 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 9.1991 (11) Å | Cell parameters from 25 reflections |
b = 7.3840 (5) Å | θ = 10.0–15.0° |
c = 25.694 (3) Å | µ = 0.08 mm−1 |
β = 100.030 (9)° | T = 296 K |
V = 1718.6 (3) Å3 | Prism, colourless |
Z = 4 | 0.40 × 0.30 × 0.24 mm |
Rigaku AFC-6S diffractometer | Rint = 0.08 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.5° |
Graphite monochromator | h = 0→10 |
ω/2θ scans | k = 0→8 |
3245 measured reflections | l = −30→30 |
3043 independent reflections | 3 standard reflections every 200 reflections |
917 reflections with I > 2σ(I) | intensity decay: <0.1% |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.242 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.1064P)2] where P = (Fo2 + 2Fc2)/3 |
3043 reflections | (Δ/σ)max < 0.001 |
217 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C21H20O3 | V = 1718.6 (3) Å3 |
Mr = 320.37 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.1991 (11) Å | µ = 0.08 mm−1 |
b = 7.3840 (5) Å | T = 296 K |
c = 25.694 (3) Å | 0.40 × 0.30 × 0.24 mm |
β = 100.030 (9)° |
Rigaku AFC-6S diffractometer | Rint = 0.08 |
3245 measured reflections | 3 standard reflections every 200 reflections |
3043 independent reflections | intensity decay: <0.1% |
917 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.242 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.18 e Å−3 |
3043 reflections | Δρmin = −0.24 e Å−3 |
217 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.7451 (4) | 0.0633 (5) | 0.06785 (14) | 0.0566 (11) | |
O2 | 0.9436 (5) | 0.2165 (6) | 0.05039 (17) | 0.0816 (15) | |
O3 | 0.4958 (5) | 0.3682 (6) | −0.04818 (16) | 0.0707 (12) | |
C1 | 0.8382 (6) | −0.0498 (7) | 0.1059 (2) | 0.0501 (14) | |
H1 | 0.9229 | 0.0203 | 0.1238 | 0.060* | |
C2 | 0.7439 (6) | −0.1098 (7) | 0.1459 (2) | 0.0480 (14) | |
H2 | 0.6572 | −0.1715 | 0.1262 | 0.058* | |
C3 | 0.8279 (7) | −0.2480 (8) | 0.1842 (2) | 0.0675 (18) | |
H3A | 0.9110 | −0.1886 | 0.2060 | 0.081* | |
H3B | 0.7633 | −0.2931 | 0.2073 | 0.081* | |
C4 | 0.8836 (7) | −0.4055 (9) | 0.1558 (3) | 0.078 (2) | |
H4A | 0.9414 | −0.4848 | 0.1816 | 0.093* | |
H4B | 0.8000 | −0.4742 | 0.1377 | 0.093* | |
C5 | 0.9774 (7) | −0.3459 (8) | 0.1161 (3) | 0.077 (2) | |
H5A | 1.0051 | −0.4506 | 0.0973 | 0.092* | |
H5B | 1.0670 | −0.2892 | 0.1344 | 0.092* | |
C6 | 0.8923 (6) | −0.2115 (8) | 0.0767 (2) | 0.0627 (17) | |
H6A | 0.8083 | −0.2720 | 0.0558 | 0.075* | |
H6B | 0.9558 | −0.1684 | 0.0529 | 0.075* | |
C7 | 0.8126 (7) | 0.1888 (8) | 0.0414 (2) | 0.0545 (16) | |
C8 | 0.7050 (6) | 0.2836 (7) | 0.0023 (2) | 0.0513 (14) | |
C9 | 0.7374 (7) | 0.4234 (8) | −0.0320 (2) | 0.0689 (18) | |
H9 | 0.8294 | 0.4740 | −0.0332 | 0.083* | |
C10 | 0.6098 (9) | 0.4669 (9) | −0.0619 (2) | 0.0760 (19) | |
H10 | 0.5989 | 0.5531 | −0.0887 | 0.091* | |
C11 | 0.5594 (7) | 0.2571 (8) | −0.0082 (2) | 0.0577 (15) | |
H11 | 0.5084 | 0.1746 | 0.0092 | 0.069* | |
C12 | 0.6878 (6) | 0.0498 (7) | 0.1748 (2) | 0.0468 (14) | |
C13 | 0.5375 (6) | 0.1068 (7) | 0.1637 (2) | 0.0446 (13) | |
C14 | 0.4291 (6) | 0.0264 (8) | 0.1265 (2) | 0.0581 (15) | |
H14 | 0.4553 | −0.0687 | 0.1062 | 0.070* | |
C15 | 0.2849 (7) | 0.0826 (9) | 0.1185 (3) | 0.0761 (19) | |
H15 | 0.2152 | 0.0261 | 0.0931 | 0.091* | |
C16 | 0.2425 (7) | 0.2252 (10) | 0.1486 (3) | 0.078 (2) | |
H16 | 0.1443 | 0.2614 | 0.1440 | 0.094* | |
C17 | 0.3437 (8) | 0.3081 (8) | 0.1837 (3) | 0.0716 (19) | |
H17 | 0.3149 | 0.4055 | 0.2025 | 0.086* | |
C18 | 0.4943 (7) | 0.2540 (7) | 0.1937 (2) | 0.0533 (15) | |
C19 | 0.5977 (9) | 0.3431 (8) | 0.2311 (2) | 0.0701 (18) | |
H19 | 0.5690 | 0.4406 | 0.2498 | 0.084* | |
C20 | 0.7396 (9) | 0.2873 (9) | 0.2400 (2) | 0.078 (2) | |
H20 | 0.8079 | 0.3452 | 0.2656 | 0.093* | |
C21 | 0.7853 (7) | 0.1430 (8) | 0.2113 (2) | 0.0611 (16) | |
H21 | 0.8844 | 0.1101 | 0.2171 | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.051 (2) | 0.065 (3) | 0.055 (2) | 0.009 (2) | 0.0110 (19) | 0.009 (2) |
O2 | 0.055 (3) | 0.095 (4) | 0.097 (4) | −0.006 (3) | 0.020 (2) | 0.026 (3) |
O3 | 0.084 (3) | 0.062 (3) | 0.061 (3) | 0.010 (3) | −0.003 (2) | 0.005 (2) |
C1 | 0.046 (3) | 0.059 (4) | 0.045 (3) | 0.006 (3) | 0.010 (3) | 0.005 (3) |
C2 | 0.046 (3) | 0.052 (3) | 0.046 (3) | 0.003 (3) | 0.008 (3) | −0.005 (3) |
C3 | 0.077 (4) | 0.059 (4) | 0.074 (4) | 0.017 (3) | 0.032 (3) | 0.013 (4) |
C4 | 0.080 (4) | 0.067 (4) | 0.091 (5) | 0.027 (4) | 0.026 (4) | 0.018 (4) |
C5 | 0.071 (4) | 0.069 (4) | 0.100 (5) | 0.020 (4) | 0.039 (4) | 0.011 (4) |
C6 | 0.065 (4) | 0.070 (4) | 0.059 (4) | 0.015 (3) | 0.029 (3) | 0.005 (3) |
C7 | 0.064 (4) | 0.055 (4) | 0.050 (4) | 0.000 (4) | 0.024 (3) | 0.000 (3) |
C8 | 0.060 (4) | 0.050 (4) | 0.045 (3) | 0.010 (3) | 0.013 (3) | 0.003 (3) |
C9 | 0.074 (5) | 0.074 (5) | 0.064 (4) | 0.009 (4) | 0.027 (4) | 0.010 (4) |
C10 | 0.108 (6) | 0.067 (4) | 0.059 (5) | 0.015 (5) | 0.031 (4) | 0.015 (4) |
C11 | 0.075 (5) | 0.049 (4) | 0.047 (4) | 0.006 (3) | 0.005 (3) | 0.006 (3) |
C12 | 0.056 (4) | 0.045 (3) | 0.043 (3) | 0.000 (3) | 0.016 (3) | 0.006 (3) |
C13 | 0.052 (3) | 0.043 (3) | 0.041 (3) | −0.003 (3) | 0.014 (3) | 0.000 (3) |
C14 | 0.055 (4) | 0.061 (4) | 0.059 (4) | 0.005 (3) | 0.012 (3) | 0.001 (3) |
C15 | 0.061 (4) | 0.079 (5) | 0.091 (5) | 0.000 (4) | 0.020 (4) | 0.000 (4) |
C16 | 0.059 (4) | 0.080 (5) | 0.101 (6) | 0.017 (4) | 0.031 (4) | 0.010 (5) |
C17 | 0.090 (5) | 0.050 (4) | 0.085 (5) | 0.017 (4) | 0.047 (4) | 0.008 (4) |
C18 | 0.072 (4) | 0.043 (4) | 0.053 (4) | 0.007 (3) | 0.031 (3) | 0.006 (3) |
C19 | 0.112 (6) | 0.049 (4) | 0.053 (4) | 0.005 (4) | 0.027 (4) | −0.007 (3) |
C20 | 0.107 (6) | 0.068 (5) | 0.056 (4) | −0.009 (5) | 0.006 (4) | −0.019 (4) |
C21 | 0.066 (4) | 0.063 (4) | 0.052 (4) | −0.005 (4) | 0.003 (3) | 0.005 (4) |
O1—C7 | 1.362 (6) | C8—C9 | 1.423 (7) |
O1—C1 | 1.448 (6) | C9—C10 | 1.326 (8) |
O2—C7 | 1.205 (6) | C9—H9 | 0.9300 |
O3—C11 | 1.364 (6) | C10—H10 | 0.9300 |
O3—C10 | 1.373 (7) | C11—H11 | 0.9300 |
C1—C2 | 1.520 (6) | C12—C21 | 1.365 (7) |
C1—C6 | 1.539 (7) | C12—C13 | 1.426 (7) |
C1—H1 | 0.9800 | C13—C14 | 1.390 (7) |
C2—C3 | 1.531 (7) | C13—C18 | 1.428 (7) |
C2—C12 | 1.530 (7) | C14—C15 | 1.371 (7) |
C2—H2 | 0.9800 | C14—H14 | 0.9300 |
C3—C4 | 1.509 (8) | C15—C16 | 1.401 (8) |
C3—H3A | 0.9700 | C15—H15 | 0.9300 |
C3—H3B | 0.9700 | C16—C17 | 1.328 (8) |
C4—C5 | 1.511 (7) | C16—H16 | 0.9300 |
C4—H4A | 0.9700 | C17—C18 | 1.421 (8) |
C4—H4B | 0.9700 | C17—H17 | 0.9300 |
C5—C6 | 1.532 (7) | C18—C19 | 1.394 (8) |
C5—H5A | 0.9700 | C19—C20 | 1.350 (8) |
C5—H5B | 0.9700 | C19—H19 | 0.9300 |
C6—H6A | 0.9700 | C20—C21 | 1.403 (8) |
C6—H6B | 0.9700 | C20—H20 | 0.9300 |
C7—C8 | 1.459 (8) | C21—H21 | 0.9300 |
C8—C11 | 1.334 (7) | ||
C7—O1—C1 | 117.6 (4) | C11—C8—C7 | 127.3 (6) |
C11—O3—C10 | 105.5 (5) | C9—C8—C7 | 125.7 (6) |
O1—C1—C2 | 106.5 (4) | C10—C9—C8 | 106.0 (6) |
O1—C1—C6 | 108.7 (4) | C10—C9—H9 | 127.0 |
C2—C1—C6 | 112.0 (4) | C8—C9—H9 | 127.0 |
O1—C1—H1 | 109.8 | C9—C10—O3 | 111.2 (6) |
C2—C1—H1 | 109.8 | C9—C10—H10 | 124.4 |
C6—C1—H1 | 109.8 | O3—C10—H10 | 124.4 |
C1—C2—C3 | 110.2 (4) | C8—C11—O3 | 110.4 (5) |
C1—C2—C12 | 112.6 (4) | C8—C11—H11 | 124.8 |
C3—C2—C12 | 112.1 (4) | O3—C11—H11 | 124.8 |
C1—C2—H2 | 107.2 | C21—C12—C13 | 119.1 (5) |
C3—C2—H2 | 107.2 | C21—C12—C2 | 119.0 (5) |
C12—C2—H2 | 107.2 | C13—C12—C2 | 121.9 (5) |
C4—C3—C2 | 112.3 (5) | C14—C13—C12 | 124.5 (5) |
C4—C3—H3A | 109.1 | C14—C13—C18 | 117.6 (5) |
C2—C3—H3A | 109.1 | C12—C13—C18 | 118.0 (5) |
C4—C3—H3B | 109.1 | C15—C14—C13 | 122.2 (6) |
C2—C3—H3B | 109.1 | C15—C14—H14 | 118.9 |
H3A—C3—H3B | 107.9 | C13—C14—H14 | 118.9 |
C5—C4—C3 | 112.5 (5) | C14—C15—C16 | 120.0 (7) |
C5—C4—H4A | 109.1 | C14—C15—H15 | 120.0 |
C3—C4—H4A | 109.1 | C16—C15—H15 | 120.0 |
C5—C4—H4B | 109.1 | C17—C16—C15 | 119.5 (6) |
C3—C4—H4B | 109.1 | C17—C16—H16 | 120.3 |
H4A—C4—H4B | 107.8 | C15—C16—H16 | 120.3 |
C4—C5—C6 | 110.4 (5) | C16—C17—C18 | 122.6 (6) |
C4—C5—H5A | 109.6 | C16—C17—H17 | 118.7 |
C6—C5—H5A | 109.6 | C18—C17—H17 | 118.7 |
C4—C5—H5B | 109.6 | C19—C18—C17 | 121.2 (6) |
C6—C5—H5B | 109.6 | C19—C18—C13 | 120.7 (6) |
H5A—C5—H5B | 108.1 | C17—C18—C13 | 118.1 (6) |
C5—C6—C1 | 110.6 (4) | C20—C19—C18 | 119.8 (6) |
C5—C6—H6A | 109.5 | C20—C19—H19 | 120.1 |
C1—C6—H6A | 109.5 | C18—C19—H19 | 120.1 |
C5—C6—H6B | 109.5 | C19—C20—C21 | 120.8 (6) |
C1—C6—H6B | 109.5 | C19—C20—H20 | 119.6 |
H6A—C6—H6B | 108.1 | C21—C20—H20 | 119.6 |
O2—C7—O1 | 123.2 (6) | C12—C21—C20 | 121.6 (6) |
O2—C7—C8 | 125.9 (6) | C12—C21—H21 | 119.2 |
O1—C7—C8 | 110.9 (5) | C20—C21—H21 | 119.2 |
C11—C8—C9 | 107.0 (5) | ||
C7—O1—C1—C2 | 154.5 (4) | C1—C2—C12—C21 | −71.7 (6) |
C7—O1—C1—C6 | −84.6 (5) | C3—C2—C12—C21 | 53.2 (6) |
O1—C1—C2—C3 | 173.5 (4) | C1—C2—C12—C13 | 106.6 (5) |
C6—C1—C2—C3 | 54.7 (6) | C3—C2—C12—C13 | −128.5 (5) |
O1—C1—C2—C12 | −60.6 (5) | C21—C12—C13—C14 | 178.1 (5) |
C6—C1—C2—C12 | −179.3 (4) | C2—C12—C13—C14 | −0.2 (8) |
C1—C2—C3—C4 | −53.7 (7) | C21—C12—C13—C18 | −3.4 (7) |
C12—C2—C3—C4 | −179.9 (5) | C2—C12—C13—C18 | 178.3 (4) |
C2—C3—C4—C5 | 55.0 (7) | C12—C13—C14—C15 | 177.8 (5) |
C3—C4—C5—C6 | −55.5 (7) | C18—C13—C14—C15 | −0.8 (8) |
C4—C5—C6—C1 | 55.5 (7) | C13—C14—C15—C16 | −0.2 (9) |
O1—C1—C6—C5 | −173.9 (4) | C14—C15—C16—C17 | 1.8 (10) |
C2—C1—C6—C5 | −56.4 (6) | C15—C16—C17—C18 | −2.4 (10) |
C1—O1—C7—O2 | −4.5 (8) | C16—C17—C18—C19 | −179.5 (6) |
C1—O1—C7—C8 | 176.5 (4) | C16—C17—C18—C13 | 1.4 (9) |
O2—C7—C8—C11 | −179.3 (6) | C14—C13—C18—C19 | −178.8 (6) |
O1—C7—C8—C11 | −0.3 (8) | C12—C13—C18—C19 | 2.5 (7) |
O2—C7—C8—C9 | 0.7 (9) | C14—C13—C18—C17 | 0.2 (7) |
O1—C7—C8—C9 | 179.7 (5) | C12—C13—C18—C17 | −178.4 (5) |
C11—C8—C9—C10 | −2.0 (6) | C17—C18—C19—C20 | 179.4 (6) |
C7—C8—C9—C10 | 178.0 (6) | C13—C18—C19—C20 | −1.6 (9) |
C8—C9—C10—O3 | 1.8 (7) | C18—C19—C20—C21 | 1.5 (10) |
C11—O3—C10—C9 | −0.9 (7) | C13—C12—C21—C20 | 3.4 (8) |
C9—C8—C11—O3 | 1.5 (6) | C2—C12—C21—C20 | −178.2 (5) |
C7—C8—C11—O3 | −178.5 (5) | C19—C20—C21—C12 | −2.5 (9) |
C10—O3—C11—C8 | −0.4 (6) |
Experimental details
Crystal data | |
Chemical formula | C21H20O3 |
Mr | 320.37 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 9.1991 (11), 7.3840 (5), 25.694 (3) |
β (°) | 100.030 (9) |
V (Å3) | 1718.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.40 × 0.30 × 0.24 |
Data collection | |
Diffractometer | Rigaku AFC-6S diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3245, 3043, 917 |
Rint | 0.08 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.242, 0.96 |
No. of reflections | 3043 |
No. of parameters | 217 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.24 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1994), SAPI91 (Fan, 1991), SHELXL97 (Sheldrick, 1997), TEXSAN.
3-Furoate trans-2-arylcyclohexanol esters were prepared as model compounds as part of an investigation to create a chiral auxiliary for use in as asymmetric intramolecular Diels–Alder reaction with a furandiene (IMDAF reaction) (Keay & Hunt, 1999). Molecular modeling had suggested that such systems might be able to block one face of the furandiene. The model compound, 2-(1-naphthyl)cyclohexyl 3-furancarboxylate, (I), was prepared and the structure determined in order to verify the molecular modeling results.
The asymmetric unit of (I) is composed of molecules (Fig. 1) which are separated by normal van der Waals distances. The molecular dimensions are normal and lie within expected values for corresponding bond distances and angles (Orpen et al., 1994). The C1–C6 cyclohexyl ring adopts a classical chair conformation, with puckering parameters (Cremer & Pople, 1975) Q = 0.563 (6) Å, θ = 177.7 (6)° and ω = 123 (21)°. The naphthyl ring is essentially planar, with the maximum deviation of any atom from the mean plane being 0.027 (4) Å. The five-membered furan ring is also planar.