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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1660.
Published online 2009 June 20. doi:  10.1107/S1600536809023162
PMCID: PMC2969198

(±)-syn-Isopropyl 4-(1,1,1,3,3,3-hexa­fluoro­propan-2-yl­oxy)-1-hydr­oxy-3-methyl-2-(prop-1-yn­yl)cyclo­pent-2-ene­carboxyl­ate

Abstract

The title compound, C16H18F6O4, was obtained through an unprecedented one-pot reaction sequence involving a Gosteli–Claisen rearrangement and a cyclo­isomerization. The constitution and relative configuration were determined by single-crystal X-ray diffraction analysis. In the crystal, mol­ecules are connected via O—H (...) O hydrogen bonds.

Related literature

For the preparation, see: Neises & Steglich (1978 [triangle]); Hiersemann (2000 [triangle]). For details of the Gosteli–Claisen rearrangement, see: Gosteli (1972 [triangle]); Landor & Black (1965 [triangle]).

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Object name is e-65-o1660-scheme1.jpg

Experimental

Crystal data

  • C16H18F6O4
  • M r = 388.30
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1660-efi1.jpg
  • a = 6.0166 (4) Å
  • b = 11.9075 (6) Å
  • c = 13.2798 (8) Å
  • α = 104.600 (5)°
  • β = 91.775 (5)°
  • γ = 96.955 (5)°
  • V = 912.03 (10) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.14 mm−1
  • T = 173 K
  • 0.42 × 0.20 × 0.18 mm

Data collection

  • Oxford Diffraction Xcalibur S CCD diffractometer
  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 [triangle]) T min = 0.944, T max = 0.975
  • 7349 measured reflections
  • 3175 independent reflections
  • 2089 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.106
  • S = 0.96
  • 3175 reflections
  • 240 parameters
  • H-atom parameters constrained
  • Δρmax = 0.27 e Å−3
  • Δρmin = −0.29 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL-Plus (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023162/hg2521sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023162/hg2521Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

For the preparation of the title compound (±)-(I) a propargyl vinyl ether (II) was synthesized from 2-butin-1-ol using an etherification with bromoacetic acid, an esterification under Steglich's conditions (Neises & Steglich, 1978) and an aldol condensation (Hiersemann, 2000). An unprecedented one-pot reaction sequence involving an uncatalyzed Gosteli-Claisen rearrangement (Gosteli, 1972) of the propargyl vinyl ether (II) (Landor & Black, 1965) and a cycloisomerization under incorporation of a solvent molecule provided (I) as a colourless solid. Fig. 1 depicts the constitution and relative configuration of the isolated diastereomer (I).

Experimental

The title compound (I) was synthesized according to the following procedure. A solution of (II) (0.044 g, 0.2 mmol) in dry hexafluoroisopropanol (0.6 ml) was stirred at 333 K for 23 h. The solvent was removed under reduced pressure. Flash chromatography (isohexane/ethyl acetate 100/1 to 50/1 to 20/1) afforded (I) as a single diastereomer (0.026 g, 0.07 mmol, 34%) and 37% of the starting material (II). Single crystals of (I) were obtained by vapor diffusion recrystallization technique from isohexane and ethyl acetate to yield colorless cuboids: mp 385 K; Rf 0.32 (cyclohexane/ethyl acetate 5/1); 1H NMR (CDCl3, 400 MHz, δ): 1.23 (d, J = 6.3 Hz, 3H, 8-H), 1.26 (d, J = 6.3 Hz, 3H, 8-H), 1.91 (s, 3H, 12-H), 2.01 (s, 3H, 11-H), 2.03 (dd, J = 13.6, 5.9 Hz, 1H, 5-H), 2.86 (dd, J = 13.6, 7.0 Hz, 1H, 5-H), 3.76 (br.s, 1H, –OH), 4.23 (sep, J = 5.9 Hz, 1H, 13-H), 4.67 (t, J = 5.9 Hz, 1H, 4-H), 5.06 (sep, J = 6.3 Hz, 1H, 7-H); 19F NMR (CDCl3, 282 MHz, δ): (-77.0)-(-76.7) (m, 6 F); 13C NMR (CDCl3, 101 MHz, δ): 4.8 (11-CH3), 13.3 (12-CH3), 21.7 (8-CH3), 21.8 (8-CH3), 42.7 (5-CH2), 70.6 (7-CH), 71.6 (9-C), 76.0 (sep, J = 32.6 Hz, 13-CH), 83.1 (1-C), 88.9 (4-CH), 94.5 (10-C), 121.2 (q, J = 283.0 Hz, 14-C), 121.8 (q, J = 283.0 Hz, 14-C), 126.5 (2-C), 146.9 (3-C), 173.6 (6-C); IR (cm-1): 3485(br,s) (ν O—H, OH in H-bridges), 2990(m) 2940(m) 2920(m) (νas,s C—H, CH2, CH3, CH), 2230(w) (ν C[equivalent]C), 1715(s) (ν C=O, ester), 1635(m) (ν C=C), 1380(m) (δs C—H, CH3), 1295(s) (ν C—O, ester), 1240(s) 1230(s) 1220(s) (ν C—F), 1185(s) 1120(s) 1105(s) (ν C—O, ether); Anal. Calcd. for C16H18F6O4: C,49.5; H, 4.7; Found: C, 49.1; H, 4.7; M = 388.30 g/mol.

Figures

Fig. 1.
The molecular structure of (I) with displacement ellipsoids shown at the 30% probability level.

Crystal data

C16H18F6O4Z = 2
Mr = 388.30F(000) = 400
Triclinic, P1Dx = 1.414 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.0166 (4) ÅCell parameters from 3408 reflections
b = 11.9075 (6) Åθ = 2.7–25.0°
c = 13.2798 (8) ŵ = 0.14 mm1
α = 104.600 (5)°T = 173 K
β = 91.775 (5)°Block, colourless
γ = 96.955 (5)°0.42 × 0.20 × 0.18 mm
V = 912.03 (10) Å3

Data collection

Oxford Diffraction Xcalibur S CCD diffractometer3175 independent reflections
Radiation source: Enhance (Mo) X-ray Source2089 reflections with I > 2σ(I)
graphiteRint = 0.026
Detector resolution: 16.0560 pixels mm-1θmax = 25.0°, θmin = 2.7°
ω scansh = −7→7
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)k = −13→14
Tmin = 0.944, Tmax = 0.975l = −15→11
7349 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H-atom parameters constrained
S = 0.96w = 1/[σ2(Fo2) + (0.0599P)2] where P = (Fo2 + 2Fc2)/3
3175 reflections(Δ/σ)max < 0.001
240 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = −0.29 e Å3

Special details

Experimental. CrysAlis RED (Oxford Diffraction 2008) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
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)

xyzUiso*/Ueq
F10.8004 (4)0.56391 (17)0.16252 (16)0.1130 (8)
F21.0918 (3)0.49063 (18)0.10772 (12)0.1036 (7)
F30.7665 (3)0.39187 (15)0.06173 (11)0.0842 (6)
F41.0556 (2)0.43622 (12)0.40071 (10)0.0537 (4)
F50.9672 (2)0.59099 (11)0.36511 (11)0.0631 (5)
F61.2566 (2)0.51846 (13)0.30212 (11)0.0608 (4)
O10.0648 (2)0.15814 (11)0.13523 (10)0.0286 (4)
H10.02640.10790.07860.043*
O20.6874 (2)0.38842 (11)0.26452 (11)0.0310 (4)
O30.1934 (2)−0.05252 (12)0.05543 (11)0.0406 (4)
O40.4173 (2)−0.03491 (12)0.19701 (11)0.0391 (4)
C10.6115 (3)0.26537 (16)0.25431 (15)0.0243 (5)
H1A0.74290.22310.26090.029*
C20.4539 (3)0.25339 (16)0.33674 (15)0.0243 (5)
C30.2714 (3)0.17686 (16)0.29615 (15)0.0231 (4)
C40.2677 (3)0.13463 (16)0.17825 (14)0.0227 (4)
C50.4762 (3)0.20733 (17)0.15116 (15)0.0293 (5)
H5A0.56610.15620.10280.035*
H5B0.43110.26730.11770.035*
C60.9030 (3)0.41341 (17)0.23280 (16)0.0299 (5)
H60.96840.33840.20980.036*
C70.8883 (5)0.4666 (2)0.1413 (2)0.0605 (8)
C81.0461 (4)0.4918 (2)0.32484 (18)0.0397 (6)
C90.5107 (3)0.31553 (18)0.44862 (15)0.0367 (6)
H9A0.39430.29020.49120.055*
H9B0.51930.40020.45740.055*
H9C0.65570.29700.47080.055*
C100.0936 (3)0.13487 (17)0.35228 (15)0.0256 (5)
C11−0.0581 (3)0.09773 (18)0.39548 (16)0.0318 (5)
C12−0.2433 (4)0.0527 (2)0.44912 (19)0.0486 (6)
H12A−0.2256−0.02700.45250.073*
H12B−0.38580.05180.41090.073*
H12C−0.24280.10320.52000.073*
C130.2847 (3)0.00474 (17)0.13700 (15)0.0237 (5)
C140.4642 (4)−0.15683 (18)0.16071 (17)0.0392 (6)
H140.3778−0.19490.09260.047*
C150.7079 (4)−0.1520 (2)0.1452 (2)0.0602 (8)
H15A0.7475−0.10450.09630.090*
H15B0.7441−0.23150.11680.090*
H15C0.7929−0.11680.21210.090*
C160.3840 (5)−0.2186 (2)0.2411 (2)0.0710 (9)
H16A0.4691−0.18190.30780.107*
H16B0.4064−0.30110.21840.107*
H16C0.2241−0.21310.24950.107*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
F10.179 (2)0.0561 (12)0.1164 (16)0.0058 (12)−0.0384 (15)0.0547 (11)
F20.1085 (14)0.1364 (17)0.0573 (11)−0.0682 (13)0.0018 (10)0.0494 (11)
F30.1084 (12)0.0924 (13)0.0418 (9)−0.0499 (10)−0.0191 (9)0.0316 (8)
F40.0516 (8)0.0668 (10)0.0425 (8)−0.0019 (7)−0.0024 (6)0.0191 (7)
F50.0721 (9)0.0333 (8)0.0679 (10)0.0027 (7)0.0029 (8)−0.0145 (7)
F60.0357 (8)0.0757 (10)0.0675 (10)−0.0151 (7)0.0060 (7)0.0220 (8)
O10.0311 (7)0.0296 (8)0.0227 (8)0.0091 (6)−0.0052 (6)0.0008 (6)
O20.0303 (8)0.0201 (7)0.0417 (9)0.0021 (6)0.0045 (6)0.0069 (6)
O30.0513 (9)0.0306 (8)0.0333 (9)0.0110 (7)−0.0156 (8)−0.0043 (7)
O40.0503 (9)0.0288 (8)0.0346 (9)0.0142 (7)−0.0144 (7)−0.0006 (7)
C10.0238 (10)0.0183 (10)0.0301 (11)0.0032 (8)0.0018 (9)0.0050 (8)
C20.0275 (10)0.0239 (10)0.0219 (11)0.0061 (8)0.0003 (9)0.0058 (8)
C30.0251 (10)0.0231 (10)0.0214 (10)0.0055 (8)0.0020 (8)0.0051 (8)
C40.0215 (10)0.0265 (10)0.0198 (10)0.0046 (8)0.0000 (8)0.0050 (8)
C50.0327 (11)0.0312 (11)0.0228 (11)−0.0001 (9)0.0052 (9)0.0065 (9)
C60.0355 (11)0.0199 (10)0.0337 (12)−0.0011 (8)0.0092 (10)0.0073 (9)
C70.0795 (19)0.0498 (18)0.0488 (17)−0.0232 (15)−0.0063 (15)0.0228 (14)
C80.0365 (13)0.0399 (14)0.0404 (14)−0.0015 (10)0.0045 (11)0.0089 (11)
C90.0404 (12)0.0375 (13)0.0276 (12)0.0012 (10)−0.0024 (10)0.0022 (10)
C100.0291 (11)0.0266 (11)0.0219 (11)0.0053 (9)−0.0001 (9)0.0070 (9)
C110.0309 (12)0.0387 (13)0.0294 (12)0.0042 (10)0.0011 (10)0.0157 (10)
C120.0402 (13)0.0657 (17)0.0502 (16)0.0040 (12)0.0107 (12)0.0342 (13)
C130.0183 (9)0.0294 (11)0.0221 (11)0.0012 (8)0.0025 (9)0.0052 (9)
C140.0536 (14)0.0256 (12)0.0372 (13)0.0147 (10)−0.0072 (11)0.0026 (10)
C150.0656 (17)0.0441 (15)0.078 (2)0.0211 (13)0.0294 (15)0.0188 (14)
C160.079 (2)0.0405 (15)0.100 (2)0.0080 (14)0.0324 (18)0.0276 (16)

Geometric parameters (Å, °)

F1—C71.302 (3)C5—H5A0.9900
F2—C71.339 (3)C5—H5B0.9900
F3—C71.329 (3)C6—C81.507 (3)
F4—C81.341 (3)C6—C71.510 (3)
F5—C81.319 (2)C6—H61.0000
F6—C81.330 (2)C9—H9A0.9800
O1—C41.419 (2)C9—H9B0.9800
O1—H10.8400C9—H9C0.9800
O2—C61.397 (2)C10—C111.192 (3)
O2—C11.452 (2)C11—C121.461 (3)
O3—C131.200 (2)C12—H12A0.9800
O4—C131.318 (2)C12—H12B0.9800
O4—C141.474 (2)C12—H12C0.9800
C1—C21.492 (3)C14—C151.483 (3)
C1—C51.528 (3)C14—C161.502 (4)
C1—H1A1.0000C14—H141.0000
C2—C31.342 (2)C15—H15A0.9800
C2—C91.492 (3)C15—H15B0.9800
C3—C101.434 (3)C15—H15C0.9800
C3—C41.517 (3)C16—H16A0.9800
C4—C131.522 (3)C16—H16B0.9800
C4—C51.541 (3)C16—H16C0.9800
C4—O1—H1109.5F5—C8—F4106.86 (19)
C6—O2—C1115.42 (14)F6—C8—F4106.70 (18)
C13—O4—C14118.33 (14)F5—C8—C6113.48 (18)
O2—C1—C2109.65 (14)F6—C8—C6112.73 (19)
O2—C1—C5112.11 (17)F4—C8—C6109.13 (18)
C2—C1—C5105.10 (14)C2—C9—H9A109.5
O2—C1—H1A110.0C2—C9—H9B109.5
C2—C1—H1A110.0H9A—C9—H9B109.5
C5—C1—H1A110.0C2—C9—H9C109.5
C3—C2—C9127.42 (19)H9A—C9—H9C109.5
C3—C2—C1110.79 (16)H9B—C9—H9C109.5
C9—C2—C1121.69 (16)C11—C10—C3177.6 (2)
C2—C3—C10126.87 (18)C10—C11—C12179.6 (2)
C2—C3—C4112.41 (17)C11—C12—H12A109.5
C10—C3—C4120.72 (15)C11—C12—H12B109.5
O1—C4—C3108.58 (14)H12A—C12—H12B109.5
O1—C4—C13108.35 (13)C11—C12—H12C109.5
C3—C4—C13114.56 (17)H12A—C12—H12C109.5
O1—C4—C5112.55 (16)H12B—C12—H12C109.5
C3—C4—C5103.23 (14)O3—C13—O4124.56 (18)
C13—C4—C5109.61 (15)O3—C13—C4122.24 (17)
C1—C5—C4106.17 (16)O4—C13—C4113.11 (15)
C1—C5—H5A110.5O4—C14—C15107.02 (18)
C4—C5—H5A110.5O4—C14—C16106.87 (18)
C1—C5—H5B110.5C15—C14—C16115.0 (2)
C4—C5—H5B110.5O4—C14—H14109.3
H5A—C5—H5B108.7C15—C14—H14109.3
O2—C6—C8108.60 (17)C16—C14—H14109.3
O2—C6—C7109.24 (18)C14—C15—H15A109.5
C8—C6—C7113.26 (19)C14—C15—H15B109.5
O2—C6—H6108.5H15A—C15—H15B109.5
C8—C6—H6108.5C14—C15—H15C109.5
C7—C6—H6108.5H15A—C15—H15C109.5
F1—C7—F3108.0 (2)H15B—C15—H15C109.5
F1—C7—F2106.8 (2)C14—C16—H16A109.5
F3—C7—F2106.9 (2)C14—C16—H16B109.5
F1—C7—C6113.5 (2)H16A—C16—H16B109.5
F3—C7—C6110.3 (2)C14—C16—H16C109.5
F2—C7—C6111.1 (2)H16A—C16—H16C109.5
F5—C8—F6107.57 (18)H16B—C16—H16C109.5
C6—O2—C1—C2149.56 (16)O2—C6—C7—F160.4 (2)
C6—O2—C1—C5−94.11 (18)C8—C6—C7—F1−60.8 (3)
O2—C1—C2—C3133.92 (16)O2—C6—C7—F3−60.9 (3)
C5—C1—C2—C313.2 (2)C8—C6—C7—F3177.9 (2)
O2—C1—C2—C9−49.5 (2)O2—C6—C7—F2−179.27 (18)
C5—C1—C2—C9−170.23 (17)C8—C6—C7—F259.6 (3)
C9—C2—C3—C10−2.3 (3)O2—C6—C8—F5−58.6 (2)
C1—C2—C3—C10173.99 (18)C7—C6—C8—F563.0 (3)
C9—C2—C3—C4178.06 (18)O2—C6—C8—F6178.82 (17)
C1—C2—C3—C4−5.6 (2)C7—C6—C8—F6−59.6 (3)
C2—C3—C4—O1−123.92 (17)O2—C6—C8—F460.5 (2)
C10—C3—C4—O156.4 (2)C7—C6—C8—F4−178.0 (2)
C2—C3—C4—C13114.83 (18)C14—O4—C13—O32.1 (3)
C10—C3—C4—C13−64.8 (2)C14—O4—C13—C4−174.52 (16)
C2—C3—C4—C5−4.3 (2)O1—C4—C13—O325.9 (2)
C10—C3—C4—C5176.06 (16)C3—C4—C13—O3147.25 (18)
O2—C1—C5—C4−134.32 (16)C5—C4—C13—O3−97.3 (2)
C2—C1—C5—C4−15.27 (19)O1—C4—C13—O4−157.37 (16)
O1—C4—C5—C1128.89 (16)C3—C4—C13—O4−36.0 (2)
C3—C4—C5—C112.02 (18)C5—C4—C13—O479.5 (2)
C13—C4—C5—C1−110.46 (17)C13—O4—C14—C15115.9 (2)
C1—O2—C6—C8−119.38 (18)C13—O4—C14—C16−120.4 (2)
C1—O2—C6—C7116.65 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O3i0.842.102.8431 (17)148

Symmetry codes: (i) −x, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2521).

References

  • Gosteli, J. (1972). Helv. Chim. Acta, 55, 451–460. [PubMed]
  • Hiersemann, M. (2000). Synthesis, pp. 1279–1290.
  • Landor, S. R. & Black, D. K. (1965). J. Chem. Soc. pp. 6784–6788.
  • Neises, B. & Steglich, W. (1978). Angew. Chem.90, 556–557.
  • Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED Oxford Diffraction Ltd, Yarnton, England.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography