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In the mol­ecule of the title compound, C13H18O3, there is a syn relationship between the two vicinal methyl groups. The six-membered ring adopts a chair conformation, with one equatorial and two axial groups, and the furyl group is almost parallel to the ketone group. Intermolecular hydrogen bonds [O—H...O=C 2.814 (3) Å] form chains along [100].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102007527/fr1367sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102007527/fr1367Isup2.hkl
Contains datablock I

CCDC reference: 188618

Comment top

Many sesquiterpenes possessing a furan ring have been isolated from plant species and among them, the furanoeremophilanes, (I), are the most abundant (Hikino & Konno, 1976; Kuroyanagi et al., 1985; Torres et al., 1999). The interesting linearly fused furo[2,3-b]decalin framework containing syn-vicinal dimethyl groups at atoms C-4a and C-5 of these compounds, together with the biological activities shown by some of them, have attracted the attention of many synthetic chemists (Irie et al., 1982; Jacobi et al., 1984; Koike et al., 1999; Miyashita et al., 1980; Tada et al., 1980; Yamakawa et al., 1983). We have designed a synthetic strategy for the basic skeleton (I), in which the key step is the preparation of compounds such as ketol (II). Since NMR analyses of (IIa) and (IIb) did not allow conclusive assignment of the relative stereochemistry of the methyl groups, we carried out the X-ray analysis of (IIa) which unequivocally established this relationship as syn.

Fig. 1 shows the molecular structure of (IIa), and selected bond distances, angles and torsion angles are listed in Table 1. The cyclohexanone ring adopts a chair conformation with the C3-methyl and the C2-hydroxymethyl groups in anti-diaxial orientations. This is an unexpected and unusual result since, in principle, the anti-diequatorial conformer, (IIa') (obtained by flipping the cyclohexanone ring), should be more stable.

The carbonyl and methyl (C8) groups on C2 are almost coplanar, with a O1—C1—C2—C8 torsion angle of -1.8 (4)° and the mean deviation from the plane of the four atoms being 0.007 Å, and the hydroxy moiety C2—-C7—O2 is almost perpendicular [86.84 (14)°] to this four-atom plane. This geometry does not allow intramolecular hydrogen bonding between the hydroxy and ketone groups. The fragment C1(O1)—C2—C6 of the cyclohexanone ring is practically planar, within experimental error [the maximum deviation from the plane is -0.020 (3) for atom C1] and the C1\dn O1 bond distance [1.227 (3) Å] is within the normal range. Similar results are found in previously reported cyclohexanones (Barluenga et al., 1993; Brunner & Maas, 1995; Hernández-Ortega et al., 2001; Rowland et al., 1998).

The furyl group is essentially planar, within experimental error (the mean deviation from the plane is 0.0018 Å). This group is almost parallel to the ketone group [12.82 (9)°] and is inclined at an angle of 47.23 (17)° with respect to the best plane described by atoms C2, C3, C5 and C6 of the cyclohexanone ring (the mean deviation from this pane is 0.0051 Å).

The molecules are stacked in the crystal along the a axis, with the cyclohexanone and furyl groups almost perpendicular to the ac plane (Fig. 2). The molecules are linked by intermolecular hydrogen bonds between the hydroxy and ring carbonyl groups (Table 2). The preference for intermolecular as opposed to intramolecular hydrogen bonding is due to the orientation of the (3-furyl)(hydroxy)methyl group on the cyclohexanone ring.

Experimental top

A solution of 2-methyl-2-cyclohexenone (15 mmol) in anhydrous ether (15 ml) was added dropwise to a stirred solution of lithium dimethylcuprate (30 mmol) in anhydrous ether (200 ml) at 268 K under a nitrogen atmosphere. A yellow precipitate was obtained, and after stirring for 30 min, a 1 M ethereal solution of zinc chloride (30 ml) was added, followed by a solution of furan-3-carbaldehyde (18.75 mmol) in anhydrous ether (15 ml). Stirring was continued for 15 min at 268 K, and the reaction mixture was poured into 20% aqueous ammonium chloride (350 ml). After separation, the aqueous phase was extracted with ether (2 × 30 ml). The combined ethereal phases were washed with 10% aqueous ammonium chloride (2 × 30 ml), brine (2 × 30 ml), dried and concentrated. The crude product was separated by column chromatography, yielding two compounds. The most polar product [(IIa) in 28% yield] was obtained as colorless prisms (m.p. 360–361 K) after purification and recrystallization from ether–hexane. The epimeric stereochemical relationship between (IIa) and (IIb) was established by oxidation (Jones) of each diastereoisomer to the same β-diketone.

Refinement top

The positional parameters of the hydroxy H atom were refined, while those of the other H atoms were calculated geometrically (C—H = 0.93–0.98 Å). All H atoms were fixed with Uiso = 1.2Uew of the attached non-H atom. The absolute configuration could not be determined.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (IIa), showing the atom-labelling scheme. Displacement ellipsoids are shown at the 50% probability level.
[Figure 2] Fig. 2. The crystal packing of (IIa) projected on to the ab plane. The intermolecular hydrogen bonds are along the a axis.
2-[(3-Furyl)(hydroxy)methyl]-2,3-dimethylcyclohexanone top
Crystal data top
C13H18O3Dx = 1.187 Mg m3
Mr = 222.27Melting point = 360–361 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 512 reflections
a = 7.962 (3) Åθ = 2.7–29.1°
b = 8.249 (4) ŵ = 0.08 mm1
c = 18.931 (9) ÅT = 293 K
V = 1243.3 (10) Å3Prism, colorless
Z = 40.24 × 0.20 × 0.14 mm
F(000) = 480
Data collection top
Bruker CCD area-detector
diffractometer
1045 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.149
Graphite monochromatorθmax = 27.5°, θmin = 2.2°
ϕ and ω scansh = 1010
11179 measured reflectionsk = 1010
1667 independent reflectionsl = 2424
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 0.99 w = 1/[σ2(Fo2) + (0.0271P)2]
where P = (Fo2 + 2Fc2)/3
1667 reflections(Δ/σ)max = 0.021
149 parametersΔρmax = 0.15 e Å3
0 restraintsΔρmin = 0.12 e Å3
Crystal data top
C13H18O3V = 1243.3 (10) Å3
Mr = 222.27Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.962 (3) ŵ = 0.08 mm1
b = 8.249 (4) ÅT = 293 K
c = 18.931 (9) Å0.24 × 0.20 × 0.14 mm
Data collection top
Bruker CCD area-detector
diffractometer
1045 reflections with I > 2σ(I)
11179 measured reflectionsRint = 0.149
1667 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 0.99Δρmax = 0.15 e Å3
1667 reflectionsΔρmin = 0.12 e Å3
149 parameters
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
xyzUiso*/Ueq
O10.0547 (2)0.7757 (3)0.10759 (12)0.0733 (7)
O20.2303 (3)0.6215 (3)0.00156 (11)0.0610 (6)
H20.287 (4)0.644 (3)0.0319 (15)0.061 (11)*
C10.0978 (4)0.7891 (3)0.11498 (16)0.0543 (7)
C20.2099 (3)0.6414 (3)0.12763 (14)0.0496 (7)
C30.3079 (4)0.6697 (4)0.19776 (16)0.0627 (8)
H30.39420.58520.20080.075*
C40.3997 (4)0.8345 (4)0.1983 (2)0.0823 (11)
H4A0.45490.84900.24350.099*
H4B0.48550.83450.16190.099*
C50.2803 (5)0.9755 (4)0.1856 (2)0.0874 (12)
H5A0.34391.07560.18290.105*
H5B0.20280.98410.22500.105*
C60.1809 (4)0.9516 (3)0.1167 (2)0.0716 (10)
H6A0.09631.03570.11270.086*
H6B0.25640.96160.07670.086*
C70.3326 (3)0.6299 (3)0.06395 (15)0.0511 (7)
H70.39710.73090.06200.061*
C80.1032 (3)0.4871 (3)0.13147 (19)0.0644 (9)
H8A0.06820.45680.08480.077*
H8B0.00600.50680.16030.077*
H8C0.16840.40100.15180.077*
C90.1950 (4)0.6520 (4)0.26324 (16)0.0965 (12)
H9A0.25210.69490.30380.116*
H9B0.17010.53950.27090.116*
H9C0.09230.71070.25590.116*
O100.6957 (2)0.3527 (3)0.07977 (12)0.0755 (7)
C110.6202 (3)0.5009 (4)0.08266 (17)0.0624 (8)
H110.67590.59680.09360.075*
C120.4551 (3)0.4917 (3)0.06766 (15)0.0504 (7)
C130.4257 (4)0.3236 (3)0.05373 (18)0.0645 (8)
H130.32370.27650.04140.077*
C140.5724 (4)0.2472 (4)0.06168 (18)0.0691 (9)
H140.58780.13640.05560.083*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0525 (12)0.0876 (15)0.0797 (15)0.0032 (11)0.0070 (12)0.0100 (12)
O20.0610 (14)0.0709 (14)0.0509 (12)0.0047 (11)0.0005 (13)0.0113 (11)
C10.0532 (17)0.0607 (19)0.0491 (18)0.0001 (14)0.0011 (16)0.0009 (14)
C20.0513 (16)0.0477 (16)0.0496 (16)0.0043 (13)0.0005 (15)0.0009 (13)
C30.066 (2)0.0674 (19)0.0550 (18)0.0067 (16)0.0111 (17)0.0015 (16)
C40.079 (2)0.085 (2)0.084 (2)0.006 (2)0.021 (2)0.025 (2)
C50.096 (3)0.061 (2)0.105 (3)0.009 (2)0.001 (3)0.020 (2)
C60.075 (2)0.0487 (19)0.091 (3)0.0036 (15)0.002 (2)0.0025 (17)
C70.0528 (16)0.0461 (15)0.0543 (17)0.0121 (13)0.0063 (15)0.0041 (15)
C80.0647 (19)0.0604 (18)0.068 (2)0.0102 (16)0.0073 (17)0.0102 (17)
C90.127 (3)0.110 (3)0.053 (2)0.005 (3)0.006 (2)0.002 (2)
O100.0615 (13)0.0736 (15)0.0915 (17)0.0112 (12)0.0043 (13)0.0010 (13)
C110.0557 (17)0.0525 (17)0.079 (2)0.0034 (16)0.0073 (17)0.0020 (17)
C120.0513 (16)0.0490 (15)0.0508 (16)0.0049 (15)0.0024 (16)0.0032 (15)
C130.0597 (19)0.0564 (17)0.077 (2)0.0062 (15)0.0081 (18)0.0052 (17)
C140.083 (2)0.0523 (16)0.072 (2)0.0048 (19)0.007 (2)0.0026 (17)
Geometric parameters (Å, º) top
O1—C11.227 (3)C6—H6B0.9700
O2—C71.436 (3)C7—C121.502 (4)
O2—H20.80 (3)C7—H70.9800
C1—C61.496 (4)C8—H8A0.9600
C1—C21.529 (4)C8—H8B0.9600
C2—C81.532 (3)C8—H8C0.9600
C2—C71.554 (4)C9—H9A0.9600
C2—C31.558 (4)C9—H9B0.9600
C3—C91.538 (4)C9—H9C0.9600
C3—C41.544 (4)O10—C141.356 (3)
C3—H30.9800O10—C111.364 (3)
C4—C51.521 (4)C11—C121.347 (3)
C4—H4A0.9700C11—H110.9300
C4—H4B0.9700C12—C131.430 (4)
C5—C61.538 (5)C13—C141.335 (4)
C5—H5A0.9700C13—H130.9300
C5—H5B0.9700C14—H140.9300
C6—H6A0.9700
C7—O2—H2109 (2)H6A—C6—H6B108.0
O1—C1—C6121.4 (3)O2—C7—C12111.7 (2)
O1—C1—C2121.6 (3)O2—C7—C2106.5 (2)
C6—C1—C2116.9 (2)C12—C7—C2114.7 (2)
C1—C2—C8110.2 (2)O2—C7—H7107.9
C1—C2—C7107.1 (2)C12—C7—H7107.9
C8—C2—C7109.5 (2)C2—C7—H7107.9
C1—C2—C3107.9 (2)C2—C8—H8A109.5
C8—C2—C3111.2 (2)C2—C8—H8B109.5
C7—C2—C3110.8 (2)H8A—C8—H8B109.5
C9—C3—C4110.8 (3)C2—C8—H8C109.5
C9—C3—C2112.3 (2)H8A—C8—H8C109.5
C4—C3—C2112.0 (3)H8B—C8—H8C109.5
C9—C3—H3107.1C3—C9—H9A109.5
C4—C3—H3107.1C3—C9—H9B109.5
C2—C3—H3107.1H9A—C9—H9B109.5
C5—C4—C3112.1 (2)C3—C9—H9C109.5
C5—C4—H4A109.2H9A—C9—H9C109.5
C3—C4—H4A109.2H9B—C9—H9C109.5
C5—C4—H4B109.2C14—O10—C11105.4 (2)
C3—C4—H4B109.2C12—C11—O10111.8 (3)
H4A—C4—H4B107.9C12—C11—H11124.1
C4—C5—C6110.9 (3)O10—C11—H11124.1
C4—C5—H5A109.4C11—C12—C13104.7 (3)
C6—C5—H5A109.5C11—C12—C7126.9 (2)
C4—C5—H5B109.5C13—C12—C7128.4 (2)
C6—C5—H5B109.4C14—C13—C12107.1 (3)
H5A—C5—H5B108.0C14—C13—H13126.5
C1—C6—C5111.2 (3)C12—C13—H13126.5
C1—C6—H6A109.4C13—C14—O10111.1 (3)
C5—C6—H6A109.4C13—C14—H14124.5
C1—C6—H6B109.4O10—C14—H14124.5
C5—C6—H6B109.4
O1—C1—C2—C81.8 (4)C1—C2—C7—O256.5 (3)
C6—C1—C2—C8174.3 (3)C8—C2—C7—O263.0 (3)
O1—C1—C2—C7117.3 (3)C3—C2—C7—O2173.9 (2)
C6—C1—C2—C766.6 (3)C1—C2—C7—C12179.3 (2)
O1—C1—C2—C3123.4 (3)C8—C2—C7—C1261.2 (3)
C6—C1—C2—C352.8 (3)C3—C2—C7—C1261.9 (3)
C1—C2—C3—C973.1 (3)C14—O10—C11—C120.5 (3)
C8—C2—C3—C947.9 (3)O10—C11—C12—C130.5 (4)
C7—C2—C3—C9170.0 (3)O10—C11—C12—C7178.4 (3)
C1—C2—C3—C452.3 (3)O2—C7—C12—C11133.0 (3)
C8—C2—C3—C4173.3 (2)C2—C7—C12—C11105.6 (3)
C7—C2—C3—C464.6 (3)O2—C7—C12—C1344.4 (4)
C9—C3—C4—C569.8 (4)C2—C7—C12—C1377.0 (4)
C2—C3—C4—C556.5 (4)C11—C12—C13—C140.3 (4)
C3—C4—C5—C655.0 (4)C7—C12—C13—C14178.2 (3)
O1—C1—C6—C5122.6 (3)C12—C13—C14—O100.0 (4)
C2—C1—C6—C553.5 (4)C11—O10—C14—C130.3 (4)
C4—C5—C6—C152.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.80 (3)2.02 (3)2.814 (3)172 (3)
Symmetry code: (i) x+1/2, y+3/2, z.

Experimental details

Crystal data
Chemical formulaC13H18O3
Mr222.27
Crystal system, space groupOrthorhombic, P212121
Temperature (K)293
a, b, c (Å)7.962 (3), 8.249 (4), 18.931 (9)
V3)1243.3 (10)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.24 × 0.20 × 0.14
Data collection
DiffractometerBruker CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
11179, 1667, 1045
Rint0.149
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.098, 0.99
No. of reflections1667
No. of parameters149
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.15, 0.12

Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.

Selected geometric parameters (Å, º) top
O1—C11.227 (3)O10—C141.356 (3)
O2—C71.436 (3)O10—C111.364 (3)
C1—C21.529 (4)C11—C121.347 (3)
C2—C81.532 (3)C12—C131.430 (4)
C2—C71.554 (4)C13—C141.335 (4)
C2—C31.558 (4)
O1—C1—C6121.4 (3)C14—O10—C11105.4 (2)
O1—C1—C2121.6 (3)C12—C11—O10111.8 (3)
C6—C1—C2116.9 (2)C11—C12—C13104.7 (3)
C1—C2—C8110.2 (2)C14—C13—C12107.1 (3)
C1—C2—C7107.1 (2)C13—C14—O10111.1 (3)
O2—C7—C2106.5 (2)
O1—C1—C2—C81.8 (4)C1—C2—C7—O256.5 (3)
O1—C1—C2—C7117.3 (3)C8—C2—C7—O263.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.80 (3)2.02 (3)2.814 (3)172 (3)
Symmetry code: (i) x+1/2, y+3/2, z.
 

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