organic compounds
1-(3-Hydroxy-5,8-dimethoxy-4-methyl-1,2,3,4-tetrahydro-1,4-epoxynaphthalen-2-yl)ethan-1-one
aDepartment of Chemistry, University of Toronto, Toronto, Ontario, M5S 3H6, Canada, and bDepartment of Chemistry, University of Guelph, Guelph, Ontario, N1G 2W1, Canada
*Correspondence e-mail: alough@chem.utoronto.ca
The stereochemistry and regioschemistry (exo) of the title compound, C15H18O5, were determined by the X-ray analysis. The methoxy groups essentially lie in the plane of the benzene ring to which they are attached, as described by the C—O—C C torsion angles of −176.80 (12) and 4.67 (19)°. In the crystal, O—H⋯O hydrogen bonds and weak C—H⋯O hydrogen bonds link the molecules, forming chains of R21(8) rings along [010].
CCDC reference: 995954
Related literature
For the metal-mediated cleavage of 2-isoxazoline rings fused to bicyclic frameworks, see: Tranmer & Tam (2002). For hydrogen-bond graph-set notation, see: Bernstein et al. (1995).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2012); cell SAINT (Bruker, 2012); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
CCDC reference: 995954
10.1107/S1600536814007764/tk5301sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814007764/tk5301Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814007764/tk5301Isup3.cml
We have previously investigated the metal-mediated cleavage of 2-isoxazoline rings fused to bicyclic frameworks that are prepared in our laboratory through nitrile oxide 1,3-dipolar cycloaddition methodology (Tranmer & Tam, 2002). When expanding this study using Raney Ni, cleavage of 2-isoxazoline compound (I) (see Fig. 1) leads to the formation of β-hydroxy ketone product (II) as a single stereoisomer. The stereochemistry of the product was determined by this single-crystal X-ray analysis. Although different (exo and endo) could be formed, only the exo regioisomer (II) was formed.
The molecular structure of the title compound is shown in Fig. 2. The methoxy groups essentially lie in the plane of the benzene ring to which they are attached as described by the C15—O5—C12—C11 and C14—O4—C9—C10 torsion angles of -176.80 (12) and 4.67 (19)°. In the crystal, O—H···O hydrogen bonds and weak C—H···O hydrogen bonds link molecules forming chains of R12(8) rings (Bernstein et al., 1995) along [010] (see Fig. 3).
To an oven dried flask containing the cycloadduct (I) (60 mg, 0.21 mmol) was added methanol (5 ml), THF (5 ml) and distilled water (2 ml) and the mixture was cooled to 273–278 K using an ice bath. AlCl3 (87 mg, 0.65 mmol) was added to the cold solution in one portion and was stirred at 273 K for 15 minutes. Raney-nickel (0.52 g) was added and was stirred for 4 h at 273 K. The reaction mixture was filtered through a pad of celite, while washing with dichloromethane (20 ml). The organic layer was separated and the aqueous layer was extracted again with dichloromethane (10 ml), and the combined organic layers were dried over sodium sulfate then evaporated using rotary evaporation. The crude product was washed by hexanes (3 ml) followed by recrystallizaion in EtOAc:hexanes = 1:5 to give product (II) in 86% yield. X-ray quality crystals were grown from a solution of the title compound in EtOAc:hexanes = 1:5.
Hydrogen atoms bonded to C atoms were placed in calculated positions with C—H distances ranging from 0.95–1.00 Å and included in the
in a riding-model approximation with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl). The hydroxyl H atom was refined independently with an isotropic displacement parameter.Data collection: APEX2 (Bruker, 2012); cell
SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C15H18O5 | Dx = 1.342 Mg m−3 |
Mr = 278.29 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, Pbca | Cell parameters from 6136 reflections |
a = 10.3091 (4) Å | θ = 5.3–66.6° |
b = 9.1309 (4) Å | µ = 0.84 mm−1 |
c = 29.2552 (13) Å | T = 147 K |
V = 2753.8 (2) Å3 | Plate, colourless |
Z = 8 | 0.17 × 0.14 × 0.05 mm |
F(000) = 1184 |
Bruker Kappa APEX DUO CCD diffractometer | 2195 reflections with I > 2σ(I) |
Radiation source: Bruker ImuS with multi-layer optics | Rint = 0.021 |
ϕ and ω scans | θmax = 66.6°, θmin = 5.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −11→10 |
Tmin = 0.686, Tmax = 0.753 | k = −6→10 |
9265 measured reflections | l = −34→34 |
2368 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0532P)2 + 1.2534P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
2368 reflections | Δρmax = 0.42 e Å−3 |
189 parameters | Δρmin = −0.24 e Å−3 |
C15H18O5 | V = 2753.8 (2) Å3 |
Mr = 278.29 | Z = 8 |
Orthorhombic, Pbca | Cu Kα radiation |
a = 10.3091 (4) Å | µ = 0.84 mm−1 |
b = 9.1309 (4) Å | T = 147 K |
c = 29.2552 (13) Å | 0.17 × 0.14 × 0.05 mm |
Bruker Kappa APEX DUO CCD diffractometer | 2368 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | 2195 reflections with I > 2σ(I) |
Tmin = 0.686, Tmax = 0.753 | Rint = 0.021 |
9265 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.42 e Å−3 |
2368 reflections | Δρmin = −0.24 e Å−3 |
189 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.88037 (9) | 0.52360 (10) | 0.62898 (3) | 0.0212 (2) | |
O2 | 0.70291 (9) | 0.72212 (11) | 0.58154 (3) | 0.0259 (2) | |
O3 | 0.85382 (10) | 0.46468 (11) | 0.52476 (3) | 0.0294 (3) | |
O4 | 0.93569 (9) | 0.88101 (11) | 0.72203 (3) | 0.0267 (2) | |
O5 | 1.28252 (9) | 0.59024 (12) | 0.60787 (3) | 0.0315 (3) | |
C1 | 0.99163 (13) | 0.55891 (15) | 0.60115 (4) | 0.0212 (3) | |
H1A | 1.0361 | 0.4727 | 0.5871 | 0.025* | |
C2 | 0.85197 (12) | 0.67220 (14) | 0.64418 (4) | 0.0192 (3) | |
C3 | 0.73874 (13) | 0.67520 (16) | 0.67653 (4) | 0.0250 (3) | |
H3A | 0.7645 | 0.6323 | 0.7059 | 0.038* | |
H3B | 0.6669 | 0.6185 | 0.6636 | 0.038* | |
H3C | 0.7109 | 0.7767 | 0.6813 | 0.038* | |
C4 | 0.83079 (12) | 0.74951 (14) | 0.59729 (4) | 0.0194 (3) | |
H4A | 0.8488 | 0.8569 | 0.5994 | 0.023* | |
C5 | 0.93447 (13) | 0.66931 (14) | 0.56674 (4) | 0.0204 (3) | |
H5A | 1.0027 | 0.7399 | 0.5566 | 0.025* | |
C6 | 0.87214 (13) | 0.59612 (15) | 0.52575 (4) | 0.0230 (3) | |
C7 | 0.84055 (16) | 0.69186 (18) | 0.48585 (5) | 0.0328 (4) | |
H7A | 0.7895 | 0.6362 | 0.4636 | 0.049* | |
H7B | 0.9211 | 0.7256 | 0.4715 | 0.049* | |
H7C | 0.7903 | 0.7766 | 0.4963 | 0.049* | |
C8 | 0.98548 (13) | 0.71876 (14) | 0.66166 (4) | 0.0192 (3) | |
C9 | 1.02832 (13) | 0.81205 (14) | 0.69594 (4) | 0.0212 (3) | |
C10 | 1.16170 (14) | 0.82634 (16) | 0.70211 (5) | 0.0259 (3) | |
H10A | 1.1935 | 0.8868 | 0.7261 | 0.031* | |
C11 | 1.24964 (14) | 0.75349 (16) | 0.67375 (5) | 0.0276 (3) | |
H11A | 1.3401 | 0.7656 | 0.6786 | 0.033* | |
C12 | 1.20648 (13) | 0.66370 (15) | 0.63864 (5) | 0.0242 (3) | |
C13 | 1.07345 (13) | 0.64562 (15) | 0.63424 (4) | 0.0213 (3) | |
C14 | 0.98079 (15) | 0.98213 (16) | 0.75556 (5) | 0.0299 (3) | |
H14A | 0.9064 | 1.0277 | 0.7708 | 0.045* | |
H14B | 1.0333 | 1.0580 | 0.7407 | 0.045* | |
H14C | 1.0337 | 0.9302 | 0.7782 | 0.045* | |
C15 | 1.41953 (14) | 0.60214 (19) | 0.61366 (6) | 0.0354 (4) | |
H15A | 1.4636 | 0.5488 | 0.5891 | 0.053* | |
H15B | 1.4443 | 0.5603 | 0.6433 | 0.053* | |
H15C | 1.4448 | 0.7055 | 0.6126 | 0.053* | |
H2O | 0.673 (2) | 0.813 (3) | 0.5676 (8) | 0.072 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0214 (5) | 0.0188 (5) | 0.0234 (5) | −0.0021 (4) | 0.0009 (4) | −0.0006 (4) |
O2 | 0.0188 (5) | 0.0323 (6) | 0.0267 (5) | 0.0002 (4) | −0.0033 (4) | −0.0005 (4) |
O3 | 0.0325 (6) | 0.0294 (6) | 0.0263 (5) | −0.0037 (4) | −0.0013 (4) | −0.0039 (4) |
O4 | 0.0249 (5) | 0.0278 (5) | 0.0274 (5) | 0.0002 (4) | −0.0040 (4) | −0.0091 (4) |
O5 | 0.0177 (5) | 0.0428 (6) | 0.0341 (6) | 0.0056 (4) | 0.0026 (4) | 0.0006 (5) |
C1 | 0.0181 (7) | 0.0226 (7) | 0.0227 (7) | 0.0012 (5) | 0.0010 (5) | −0.0012 (5) |
C2 | 0.0179 (7) | 0.0183 (7) | 0.0214 (6) | −0.0010 (5) | −0.0006 (5) | −0.0021 (5) |
C3 | 0.0199 (7) | 0.0322 (8) | 0.0229 (7) | −0.0026 (6) | 0.0019 (5) | −0.0003 (6) |
C4 | 0.0155 (6) | 0.0210 (7) | 0.0217 (7) | −0.0008 (5) | −0.0009 (5) | −0.0013 (5) |
C5 | 0.0177 (7) | 0.0215 (7) | 0.0221 (7) | 0.0000 (5) | 0.0016 (5) | 0.0001 (5) |
C6 | 0.0185 (7) | 0.0280 (8) | 0.0225 (7) | 0.0030 (5) | 0.0035 (5) | −0.0016 (6) |
C7 | 0.0397 (9) | 0.0377 (9) | 0.0211 (7) | 0.0107 (7) | −0.0001 (6) | −0.0010 (6) |
C8 | 0.0183 (7) | 0.0187 (6) | 0.0208 (6) | −0.0008 (5) | −0.0017 (5) | 0.0034 (5) |
C9 | 0.0224 (7) | 0.0198 (6) | 0.0214 (6) | −0.0005 (5) | −0.0027 (5) | 0.0021 (5) |
C10 | 0.0250 (8) | 0.0255 (7) | 0.0271 (7) | −0.0057 (6) | −0.0075 (6) | 0.0017 (6) |
C11 | 0.0185 (7) | 0.0324 (8) | 0.0319 (7) | −0.0034 (6) | −0.0059 (6) | 0.0063 (6) |
C12 | 0.0184 (7) | 0.0270 (7) | 0.0273 (7) | 0.0020 (6) | 0.0004 (5) | 0.0062 (6) |
C13 | 0.0199 (7) | 0.0215 (7) | 0.0223 (7) | 0.0008 (5) | −0.0013 (5) | 0.0033 (5) |
C14 | 0.0334 (8) | 0.0292 (7) | 0.0270 (7) | −0.0034 (6) | −0.0042 (6) | −0.0093 (6) |
C15 | 0.0171 (8) | 0.0468 (10) | 0.0422 (9) | 0.0059 (7) | 0.0030 (6) | 0.0146 (7) |
O1—C1 | 1.4431 (16) | C5—C6 | 1.5157 (18) |
O1—C2 | 1.4576 (16) | C5—H5A | 1.0000 |
O2—C4 | 1.4187 (16) | C6—C7 | 1.494 (2) |
O2—H2O | 0.97 (3) | C7—H7A | 0.9800 |
O3—C6 | 1.2153 (18) | C7—H7B | 0.9800 |
O4—C9 | 1.3750 (17) | C7—H7C | 0.9800 |
O4—C14 | 1.4252 (16) | C8—C13 | 1.3827 (19) |
O5—C12 | 1.3692 (17) | C8—C9 | 1.3880 (19) |
O5—C15 | 1.4268 (18) | C9—C10 | 1.393 (2) |
C1—C13 | 1.5086 (19) | C10—C11 | 1.397 (2) |
C1—C5 | 1.5417 (18) | C10—H10A | 0.9500 |
C1—H1A | 1.0000 | C11—C12 | 1.387 (2) |
C2—C3 | 1.5030 (18) | C11—H11A | 0.9500 |
C2—C8 | 1.5286 (18) | C12—C13 | 1.387 (2) |
C2—C4 | 1.5581 (18) | C14—H14A | 0.9800 |
C3—H3A | 0.9800 | C14—H14B | 0.9800 |
C3—H3B | 0.9800 | C14—H14C | 0.9800 |
C3—H3C | 0.9800 | C15—H15A | 0.9800 |
C4—C5 | 1.5740 (18) | C15—H15B | 0.9800 |
C4—H4A | 1.0000 | C15—H15C | 0.9800 |
C1—O1—C2 | 97.11 (9) | C6—C7—H7A | 109.5 |
C4—O2—H2O | 106.0 (14) | C6—C7—H7B | 109.5 |
C9—O4—C14 | 116.88 (11) | H7A—C7—H7B | 109.5 |
C12—O5—C15 | 116.83 (12) | C6—C7—H7C | 109.5 |
O1—C1—C13 | 101.51 (10) | H7A—C7—H7C | 109.5 |
O1—C1—C5 | 102.17 (10) | H7B—C7—H7C | 109.5 |
C13—C1—C5 | 106.84 (11) | C13—C8—C9 | 120.45 (12) |
O1—C1—H1A | 114.9 | C13—C8—C2 | 105.20 (11) |
C13—C1—H1A | 114.9 | C9—C8—C2 | 134.34 (12) |
C5—C1—H1A | 114.9 | O4—C9—C8 | 117.45 (12) |
O1—C2—C3 | 111.41 (11) | O4—C9—C10 | 124.81 (12) |
O1—C2—C8 | 100.38 (10) | C8—C9—C10 | 117.72 (13) |
C3—C2—C8 | 118.92 (11) | C9—C10—C11 | 121.26 (13) |
O1—C2—C4 | 100.44 (10) | C9—C10—H10A | 119.4 |
C3—C2—C4 | 115.93 (11) | C11—C10—H10A | 119.4 |
C8—C2—C4 | 107.14 (10) | C12—C11—C10 | 120.85 (13) |
C2—C3—H3A | 109.5 | C12—C11—H11A | 119.6 |
C2—C3—H3B | 109.5 | C10—C11—H11A | 119.6 |
H3A—C3—H3B | 109.5 | O5—C12—C13 | 116.53 (12) |
C2—C3—H3C | 109.5 | O5—C12—C11 | 126.35 (13) |
H3A—C3—H3C | 109.5 | C13—C12—C11 | 117.12 (13) |
H3B—C3—H3C | 109.5 | C8—C13—C12 | 122.49 (13) |
O2—C4—C2 | 109.65 (10) | C8—C13—C1 | 105.01 (11) |
O2—C4—C5 | 111.38 (10) | C12—C13—C1 | 132.43 (13) |
C2—C4—C5 | 101.19 (10) | O4—C14—H14A | 109.5 |
O2—C4—H4A | 111.4 | O4—C14—H14B | 109.5 |
C2—C4—H4A | 111.4 | H14A—C14—H14B | 109.5 |
C5—C4—H4A | 111.4 | O4—C14—H14C | 109.5 |
C6—C5—C1 | 112.97 (11) | H14A—C14—H14C | 109.5 |
C6—C5—C4 | 111.50 (11) | H14B—C14—H14C | 109.5 |
C1—C5—C4 | 101.12 (10) | O5—C15—H15A | 109.5 |
C6—C5—H5A | 110.3 | O5—C15—H15B | 109.5 |
C1—C5—H5A | 110.3 | H15A—C15—H15B | 109.5 |
C4—C5—H5A | 110.3 | O5—C15—H15C | 109.5 |
O3—C6—C7 | 121.69 (13) | H15A—C15—H15C | 109.5 |
O3—C6—C5 | 121.34 (12) | H15B—C15—H15C | 109.5 |
C7—C6—C5 | 116.90 (12) | ||
C2—O1—C1—C13 | 52.14 (11) | C3—C2—C8—C9 | −27.1 (2) |
C2—O1—C1—C5 | −58.12 (11) | C4—C2—C8—C9 | 106.73 (16) |
C1—O1—C2—C3 | −178.08 (10) | C14—O4—C9—C8 | −176.91 (12) |
C1—O1—C2—C8 | −51.22 (11) | C14—O4—C9—C10 | 4.67 (19) |
C1—O1—C2—C4 | 58.56 (10) | C13—C8—C9—O4 | −179.83 (11) |
O1—C2—C4—O2 | 81.46 (11) | C2—C8—C9—O4 | 1.0 (2) |
C3—C2—C4—O2 | −38.70 (15) | C13—C8—C9—C10 | −1.29 (19) |
C8—C2—C4—O2 | −174.15 (10) | C2—C8—C9—C10 | 179.56 (13) |
O1—C2—C4—C5 | −36.26 (11) | O4—C9—C10—C11 | −179.33 (12) |
C3—C2—C4—C5 | −156.42 (11) | C8—C9—C10—C11 | 2.2 (2) |
C8—C2—C4—C5 | 68.13 (12) | C9—C10—C11—C12 | −0.4 (2) |
O1—C1—C5—C6 | −85.45 (12) | C15—O5—C12—C13 | −176.80 (12) |
C13—C1—C5—C6 | 168.38 (11) | C15—O5—C12—C11 | 2.9 (2) |
O1—C1—C5—C4 | 33.82 (12) | C10—C11—C12—O5 | 177.95 (13) |
C13—C1—C5—C4 | −72.35 (12) | C10—C11—C12—C13 | −2.4 (2) |
O2—C4—C5—C6 | 5.64 (15) | C9—C8—C13—C12 | −1.6 (2) |
C2—C4—C5—C6 | 122.10 (11) | C2—C8—C13—C12 | 177.80 (12) |
O2—C4—C5—C1 | −114.69 (11) | C9—C8—C13—C1 | −178.95 (11) |
C2—C4—C5—C1 | 1.77 (12) | C2—C8—C13—C1 | 0.42 (13) |
C1—C5—C6—O3 | 10.24 (18) | O5—C12—C13—C8 | −176.91 (12) |
C4—C5—C6—O3 | −102.85 (14) | C11—C12—C13—C8 | 3.4 (2) |
C1—C5—C6—C7 | −166.79 (12) | O5—C12—C13—C1 | −0.3 (2) |
C4—C5—C6—C7 | 80.12 (15) | C11—C12—C13—C1 | 179.95 (13) |
O1—C2—C8—C13 | 31.93 (12) | O1—C1—C13—C8 | −33.15 (13) |
C3—C2—C8—C13 | 153.61 (12) | C5—C1—C13—C8 | 73.48 (13) |
C4—C2—C8—C13 | −72.51 (12) | O1—C1—C13—C12 | 149.85 (14) |
O1—C2—C8—C9 | −148.83 (14) | C5—C1—C13—C12 | −103.52 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O3i | 0.97 (3) | 1.89 (2) | 2.8295 (15) | 162 (2) |
C7—H7C···O3i | 0.98 | 2.42 | 3.3936 (19) | 173 |
Symmetry code: (i) −x+3/2, y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O3i | 0.97 (3) | 1.89 (2) | 2.8295 (15) | 162 (2) |
C7—H7C···O3i | 0.98 | 2.42 | 3.3936 (19) | 173 |
Symmetry code: (i) −x+3/2, y+1/2, z. |
Acknowledgements
This work was supported by the Natural Sciences and Engineering Research Council of Canada (NSERC).
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