organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890
Volume 71| Part 10| October 2015| Pages o710-o711

Crystal structure of 3a,6,6,9a-tetra­methyl­dodeca­hydro­naphtho­[2,1-b]furan-2-ol

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aXi'an Botanical Garden, Institute of Botany of Shaanxi Province, Xi'an 710061, People's Republic of China, and bLab for Pesticide Synthesis, Department of Pesticide Science, College of Plant Protection, Nanjing Agricultural University, Weigang 1, Xuanwu District, Nanjing 210095, People's Republic of China
*Correspondence e-mail: saintkun001@njau.edu.cn

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 29 August 2015; accepted 2 September 2015; online 12 September 2015)

The title compound (common name: sclaral), C16H28O2, is a sclareolide derivative, which was synthesized from sclareolide itself. In the mol­ecule, the two six-membered rings, A and B, of the labdane skeleton adopt chair conformations and the five-membered O-containing heterocyclic ring C displays an envelope conformation, with the methine C atom of the fused C—C bond as the flap. In the crystal, mol­ecules are linked by O—H⋯O hydrogen bonds, forming chains propagating along [100].

1. Related literature

For the chemistry and biological importance of sclareolides and the title compound, see: Dixon et al. (2012[Dixon, D. D., Lockner, J. W., Zhou, Q. & Baran, P. S. (2012). J. Am. Chem. Soc. 134, 8432-8435.]); Michaudel et al. (2015[Michaudel, Q., Ishihara, Y. & Baran, P. S. (2015). Acc. Chem. Res. 48, 712-721.]); Sun et al. (2013[Sun, Y., Li, R., Zhang, W. & Li, A. (2013). Angew. Chem. Int. Ed. 52, 9201-9204.]). For previously reported spectroscopic and anal­yt­ical data for the title compound, see: Margaros et al. (2007[Margaros, I., Montagnon, T. & Vassilikogiannakis, G. (2007). Org. Lett. 9, 5585-5588.]). For related structures, see: Martínez-Carrera et al. (1978[Martínez-Carrera, S., Martínez-Ripoll, M. & García-Blanco, S. (1978). Acta Cryst. B34, 1381-1383.]); Huang et al. (2008[Huang, Q.-C., Li, B.-G., Xie, Y.-P., Yu, K.-B. & Zhang, G.-L. (2008). Acta Cryst. E64, o1765.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C16H28O2

  • Mr = 252.38

  • Orthorhombic, P 21 21 21

  • a = 7.1675 (8) Å

  • b = 11.2654 (13) Å

  • c = 18.144 (2) Å

  • V = 1465.0 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.07 mm−1

  • T = 296 K

  • 0.22 × 0.20 × 0.18 mm

2.2. Data collection

  • Bruker SMART CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2002[Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.984, Tmax = 0.987

  • 9607 measured reflections

  • 2658 independent reflections

  • 2299 reflections with I > 2σ(I)

  • Rint = 0.030

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.127

  • S = 1.08

  • 2658 reflections

  • 181 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.40 e Å−3

  • Δρmin = −0.20 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H1O⋯O1i 0.93 (2) 1.90 (2) 2.773 (2) 155 (3)
Symmetry code: (i) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1].

Data collection: SMART (Bruker, 2002[Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2002[Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

The title compound, sclaral, is an important reaction inter­mediate in the synthesis of some natural products. It is used as a precursor of borono-sclareolide which makes the direct coupling of a terpenoid "donor" with a non-terpenoid "acceptor" possible (Dixon et al., 2012). It is also used to produce analogs of hongoquercin A, an anti­biotic of fungal origin (Michaudel et al., 2015; Sun et al., 2013). Moreover, sclaral is an inter­mediate in the production of important natural products, such as (+)-premnalane A (Margaros et al., 2007). The title compound has been synthesized and we report herein on its crystal structure,

The molecular structure of the title compound is shown in Fig. 1. The molecule possesses a highly rigid structure, composed of three main rings (A/i>, B and C). The six-membered rings, A/i> (C5/C6/C8—C11) and B (C1—C6), adopt chair conformations, while the five-membered O-containing heterocyclic ring C (C1/C2/C14/C15/O1) displays an envelope conformation, in which atom C1 is the flap.

In the crystal, molecules are linked via O—H···O hydrogen bonds forming chains propagating along the a axis direction (Table 1 and Fig. 2).

Synthesis and crystallization top

A solution of (+)-sclareolide (10.0 g, 40.0 mmol,1.0 eq) in CH2Cl2 (100ml) was cooled to 195 K and DIBAL-H (1.5M in toluene,32ml, 48.0 mmol, 1.2 eq) was added drop wise over 20 min, and stirring was continued for an additional 60 min. Water was then slowly added until the bubbles vanished then the temperature of the mixture was allow to rise to rt. the mixture was stirred at rt for 30min, and then extracted with CH2Cl2 (3 × 100 ml). The combined organic extracts were washed with saturated aqueous NaHCO3 solution (3 × 50 ml) and washed with brine (3 × 50 ml), dried over MgSO4, filtered and concentrated under reduced pressure, affording the title compound, sclaral (yield: 9.37 g, 93 %, 3.7:1 lactol:aldehyde) as a white solid. Spectroscopic and analytical data matches reported previously (Margaros et al., 2007). The white solid was recrystallized from EtOH to afford colourless crystals.

Refinement top

The CH H atoms (H1, H5 and H15) and the hydroxyl H atom (H1O) were located in a difference Fourier map. The CH H atoms were freely refined while the OH H atom was refined with Uiso(H) = 1.5Ueq(O). The remaining C-bound H atoms were placed in calculated positions and refined as riding: C—H = 0.96-0.97 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.

Related literature top

For the chemistry and biological importance of sclareolides and the title compound, see: Dixon et al. (2012); Michaudel et al. (2015); Sun et al. (2013). For the spectroscopic and analytical data of the title compound, reported previously, see: Margaros et al. (2007). For related structures, see: Martínez-Carrera et al. (1978); Huang et al. (2008).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. View along the a axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1), and C-bound H atoms have been omitted for clarity.
3a,6,6,9a-Tetramethyldodecahydronaphtho[2,1-b]furan-2-ol top
Crystal data top
C16H28O2F(000) = 560
Mr = 252.38Dx = 1.144 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2540 reflections
a = 7.1675 (8) Åθ = 3.1–21.6°
b = 11.2654 (13) ŵ = 0.07 mm1
c = 18.144 (2) ÅT = 296 K
V = 1465.0 (3) Å3Block, colourless
Z = 40.22 × 0.20 × 0.18 mm
Data collection top
Bruker SMART CCD
diffractometer
2658 independent reflections
Radiation source: fine-focus sealed tube2299 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
phi and ω scansθmax = 25.3°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 88
Tmin = 0.984, Tmax = 0.987k = 1313
9607 measured reflectionsl = 2116
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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0651P)2 + 0.258P]
where P = (Fo2 + 2Fc2)/3
2658 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.40 e Å3
1 restraintΔρmin = 0.19 e Å3
Crystal data top
C16H28O2V = 1465.0 (3) Å3
Mr = 252.38Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.1675 (8) ŵ = 0.07 mm1
b = 11.2654 (13) ÅT = 296 K
c = 18.144 (2) Å0.22 × 0.20 × 0.18 mm
Data collection top
Bruker SMART CCD
diffractometer
2658 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
2299 reflections with I > 2σ(I)
Tmin = 0.984, Tmax = 0.987Rint = 0.030
9607 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0461 restraint
wR(F2) = 0.127H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.40 e Å3
2658 reflectionsΔρmin = 0.19 e Å3
181 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
C10.0482 (3)0.86847 (19)0.67801 (12)0.0348 (5)
C20.2058 (3)0.8474 (2)0.62309 (12)0.0392 (5)
C30.3421 (3)0.7594 (2)0.65591 (13)0.0469 (6)
H3A0.44880.75040.62350.056*
H3B0.28250.68260.66120.056*
C40.4067 (3)0.8050 (2)0.73202 (13)0.0443 (5)
H4A0.49010.74710.75390.053*
H4B0.47590.87830.72550.053*
C50.2429 (3)0.82737 (18)0.78462 (12)0.0342 (5)
C60.1029 (3)0.91962 (17)0.75332 (11)0.0339 (5)
C70.1778 (4)1.04780 (19)0.74731 (14)0.0515 (6)
H7A0.11001.08960.70980.077*
H7B0.30781.04590.73470.077*
H7C0.16201.08750.79370.077*
C80.0711 (3)0.9208 (3)0.80299 (14)0.0519 (6)
H8A0.15410.98360.78690.062*
H8B0.13680.84600.79760.062*
C90.0233 (4)0.9397 (3)0.88443 (15)0.0655 (8)
H9A0.02831.01860.89100.079*
H9B0.13630.93430.91360.079*
C100.1147 (4)0.8493 (3)0.91114 (14)0.0620 (8)
H10A0.05600.77170.90970.074*
H10B0.14440.86650.96220.074*
C110.2970 (3)0.8434 (2)0.86729 (13)0.0462 (6)
C120.4061 (5)0.7330 (3)0.89311 (17)0.0775 (9)
H12A0.53230.73770.87560.116*
H12B0.34800.66280.87380.116*
H12C0.40590.72980.94600.116*
C130.4176 (4)0.9519 (3)0.88354 (15)0.0579 (7)
H13A0.51980.95470.84940.087*
H13B0.46520.94680.93290.087*
H13C0.34381.02260.87860.087*
C140.1012 (4)0.9213 (2)0.62815 (14)0.0520 (6)
H14A0.07391.00330.61570.062*
H14B0.22400.91660.65040.062*
C150.0850 (3)0.8402 (2)0.56099 (14)0.0495 (6)
H150.112 (4)0.884 (2)0.5155 (15)0.059*
C160.3106 (4)0.9544 (3)0.59153 (15)0.0622 (7)
H16A0.37430.93130.54720.093*
H16B0.39970.98230.62700.093*
H16C0.22341.01660.58050.093*
H10.007 (3)0.7879 (18)0.6884 (10)0.024 (5)*
H50.168 (3)0.751 (2)0.7848 (12)0.040 (6)*
O10.1024 (2)0.79612 (16)0.56104 (8)0.0520 (5)
O20.2051 (3)0.7454 (2)0.56902 (11)0.0678 (6)
H1O0.242 (4)0.715 (3)0.5234 (11)0.081*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0291 (10)0.0358 (11)0.0396 (11)0.0007 (9)0.0009 (9)0.0037 (9)
C20.0342 (10)0.0491 (12)0.0342 (11)0.0040 (10)0.0055 (10)0.0055 (10)
C30.0352 (11)0.0571 (14)0.0485 (14)0.0072 (11)0.0082 (11)0.0129 (11)
C40.0313 (10)0.0529 (13)0.0485 (14)0.0097 (10)0.0001 (10)0.0055 (10)
C50.0331 (10)0.0328 (10)0.0368 (11)0.0020 (9)0.0018 (9)0.0018 (9)
C60.0270 (9)0.0355 (10)0.0393 (11)0.0012 (9)0.0011 (9)0.0073 (9)
C70.0607 (15)0.0336 (12)0.0601 (15)0.0041 (11)0.0055 (13)0.0088 (11)
C80.0304 (11)0.0749 (16)0.0503 (14)0.0045 (11)0.0059 (11)0.0221 (13)
C90.0430 (13)0.104 (2)0.0498 (15)0.0091 (15)0.0137 (12)0.0322 (16)
C100.0613 (16)0.090 (2)0.0352 (13)0.0243 (16)0.0041 (13)0.0063 (13)
C110.0474 (13)0.0528 (13)0.0385 (12)0.0035 (11)0.0058 (11)0.0025 (10)
C120.092 (2)0.078 (2)0.0620 (18)0.0127 (19)0.0247 (18)0.0158 (15)
C130.0434 (13)0.0751 (17)0.0551 (15)0.0065 (13)0.0103 (13)0.0149 (14)
C140.0439 (13)0.0601 (15)0.0520 (14)0.0096 (12)0.0092 (12)0.0063 (12)
C150.0407 (12)0.0673 (15)0.0404 (13)0.0035 (12)0.0050 (11)0.0024 (12)
C160.0648 (16)0.0754 (18)0.0463 (14)0.0191 (15)0.0090 (14)0.0086 (13)
O10.0417 (8)0.0749 (11)0.0393 (9)0.0020 (9)0.0020 (8)0.0166 (8)
O20.0591 (11)0.0950 (15)0.0494 (11)0.0205 (11)0.0057 (10)0.0045 (10)
Geometric parameters (Å, º) top
C1—C141.523 (3)C6—C81.539 (3)
C1—C21.525 (3)C6—C71.544 (3)
C1—C61.534 (3)C8—C91.532 (4)
C2—O11.466 (3)C9—C101.500 (4)
C2—C31.513 (3)C10—C111.531 (3)
C2—C161.531 (3)C11—C131.526 (3)
C3—C41.544 (3)C11—C121.542 (4)
C4—C51.534 (3)C14—C151.527 (3)
C5—C61.552 (3)C15—O21.380 (3)
C5—C111.560 (3)C15—O11.432 (3)
C14—C1—C2101.16 (18)C1—C6—C5103.87 (16)
C14—C1—C6124.19 (19)C8—C6—C5108.38 (18)
C2—C1—C6116.81 (16)C7—C6—C5115.30 (17)
O1—C2—C3111.75 (18)C9—C8—C6112.63 (18)
O1—C2—C1100.87 (15)C10—C9—C8111.4 (2)
C3—C2—C1108.84 (18)C9—C10—C11115.1 (2)
O1—C2—C16105.71 (18)C13—C11—C10110.4 (2)
C3—C2—C16110.26 (19)C13—C11—C12107.4 (2)
C1—C2—C16119.00 (19)C10—C11—C12108.0 (2)
C2—C3—C4109.12 (18)C13—C11—C5114.8 (2)
C5—C4—C3112.42 (17)C10—C11—C5107.00 (18)
C4—C5—C6112.15 (17)C12—C11—C5109.0 (2)
C4—C5—C11115.27 (17)C1—C14—C15100.75 (19)
C6—C5—C11115.79 (17)O2—C15—O1108.5 (2)
C1—C6—C8108.51 (17)O2—C15—C14109.4 (2)
C1—C6—C7112.17 (19)O1—C15—C14106.16 (19)
C8—C6—C7108.36 (19)C15—O1—C2109.75 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1O···O1i0.93 (2)1.90 (2)2.773 (2)155 (3)
Symmetry code: (i) x1/2, y+3/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1O···O1i0.934 (18)1.90 (2)2.773 (2)155 (3)
Symmetry code: (i) x1/2, y+3/2, z+1.
 

Acknowledgements

This project was supported by the National Natural Science Foundation of China (Nos. 3140177 and 31200257), the West Light Foundation of The Chinese Academy of Sciences (No. 2012DF05), and the National Science Foundation of Jiangsu Province (No. BK20140684).

References

First citationBruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
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First citationHuang, Q.-C., Li, B.-G., Xie, Y.-P., Yu, K.-B. & Zhang, G.-L. (2008). Acta Cryst. E64, o1765.  CSD CrossRef IUCr Journals Google Scholar
First citationMargaros, I., Montagnon, T. & Vassilikogiannakis, G. (2007). Org. Lett. 9, 5585–5588.  CSD CrossRef PubMed CAS Google Scholar
First citationMartínez-Carrera, S., Martínez-Ripoll, M. & García-Blanco, S. (1978). Acta Cryst. B34, 1381–1383.  CSD CrossRef IUCr Journals Google Scholar
First citationMichaudel, Q., Ishihara, Y. & Baran, P. S. (2015). Acc. Chem. Res. 48, 712–721.  CrossRef CAS PubMed Google Scholar
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First citationSun, Y., Li, R., Zhang, W. & Li, A. (2013). Angew. Chem. Int. Ed. 52, 9201–9204.  CSD CrossRef CAS Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 10| October 2015| Pages o710-o711
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