(3S,4S,5R)-3-Hydr­oxy-4-methyl-5-vinyl­tetra­hydro­pyran-2-one

The title compound, C₈H₁₂O₃, was synthesized to prove the relative configuration in the projected total synthesis of curvicollides A–C. In the crystal structure, mol­ecules are linked via a bifurcated O—H...O hydrogen bond and a chain of mol­ecules is formed along the a axis.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.029
• wR factor = 0.058
• Data-to-parameter ratio = 7.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       7.21

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.48
           From the CIF: _reflns_number_total               1075
           Count of symmetry unique reflns         1079
           Completeness (_total/calc)             99.63%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4     = .          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The title compound, (I), was synthesized to proof the relative configuration in the projected total synthesis of curvicollides A—C using a catalytic asymmetric Claisen rearrangement (Abraham, Körner et al., 2004; Abraham, Körner & Hiersemann, 2004) and a diastereoselective reduction with K-Selectride (Körner & Hiersemann, 2006). In order to verify the assumed relative configuration of methyl-4-(benzyloxymethyl)-2-hydroxy-3-methylhex-5-enoate (the preparation of this intermediate will be described elsewhere; Körner & Hiersemann, 2007), the δ-lactone, (I), was prepared. Fig. 1 shows that the relative configuration of C2, C3 and C4 is as expected. The configuration of the chiral C atoms in (I) (C2 S, C3 S and C4 R) were assigned based on the previously described stereochemical course of the catalytic asymmetric Claisen rearrangement (CAC) using the chiral Lewis acid [Cu{(S,S)-tert-Butyl-box}] (H₂O)₂(SbF₆)₂ (Evans et al., 1999). In the crystal the molecules are linked via a bifurcated O—H ··· O hydrogen bridge (Table 1) and a chain of molecules is formed along the a axis.

Related literature

For related literature, see: Abraham, Körner & Hiersemann (2004); Abraham, Körner et al. (2004); Evans et al. (1999); Körner & Hiersemann (2006, 2007); Oikawa et al. (1982).

S2. Experimental

The synthesis of (I) was carried out under the conditions of the oxidative removal of the benzyl protecting group (Oikawa et al., 1982). To a solution of (2S,3S,4R)-Methyl-4-(benzyloxymethyl)-2-hydroxy-3-methylhex-5-enoate (200 mg, 0.72 mmol, 1.0 eq) in dry dichloromethane (4 ml) and pH 7 buffer (1 ml) was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.49 g, 2.16 mmol, 3.0 eq) at 273 K. The orange mixture was stirred at room temperature for 3 days and filtered through a pad of celite and MgSO₄. The solvents were removed under reduced pressure. Flash chromatography (isohexane/ethyl acetate 20/1 to 10/1) afforded (I) (78 mg, 0.49 mmol, 69%) as colourless crystals. Single crystals of (I) were obtained by vapor diffusion recrystallization technique from isohexane and ethyl acetate to yield colourless cuboids: mp 357 K; R_f = 0.5 (isohexane/ethyl acetate 1/1); ¹H NMR (400 MHz, CDCl₃, δ) 0.96 (d, J = 7.0 Hz, 3H), 2.42–2.46 (m, 1H), 2.93–2.95 (m, 1H), 3.28 (br. s, 1H), 4.20–4.35 (m, 1H + 2H), 5.10–5.21 (m, 2H), 5.68 (ddd, J = 17.4, 10.5, 6.9 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃, δ) 7.4 (CH₃), 36.0 (CH), 40.8 (CH), 69.9 (CH₂), 71.4 (CH), 118.5 (CH₂=), 133.9 (CH=), 174.2 (C═O); IR (in substance) ν 3250–3500, 2920, 1740 cm^-1; Anal. Calcd. for C₈H₁₂O₃: C, 61.5; H, 7.7. Found: C, 61.7; H, 7.7; [α]²⁵_D +18.1 (c 0.42, CHCl₃).

S3. Refinement

H atoms were refined isotropically. In the absence of significant anomalous scattering effects, Friedel pairs were merged in the final refinement.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures

Fig. 1. The molecular structure of the title compound, showing the labelling of all non-H atoms. Displacement ellipsoids are shown at the 30% probability level.

(3S,4S,5R)-3-Hydroxy-4-methyl-5-vinyltetrahydropyran-2-one

Crystal data

C8H12O3	F(000) = 336
Mr = 156.18	Dx = 1.329 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7057 reflections
a = 5.4490 (5) Å	θ = 3.3–27.5°
b = 6.4489 (5) Å	µ = 0.10 mm^−1
c = 22.2203 (14) Å	T = 173 K
V = 780.82 (11) Å^3	Block, colourless
Z = 4	0.45 × 0.40 × 0.40 mm

Data collection

Nonius KappaCCD area-detector diffractometer	727 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
Graphite monochromator	θmax = 27.5°, θmin = 3.3°
Detector resolution: 19 vertical, 18 horizontal pixels mm^-1	h = −7→7
289 frames via ω rotation (Δω = 1°) and two times 20 s per frame (three sets at different κ–angles) scans	k = −8→8
7057 measured reflections	l = −28→28
1075 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	All H-atom parameters refined
wR(F^2) = 0.058	w = 1/[σ^2(Fo^2) + (0.0305P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.90	(Δ/σ)max < 0.001
1075 reflections	Δρmax = 0.15 e Å^−3
149 parameters	Δρmin = −0.14 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.048 (5)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.5199 (2)	0.8726 (2)	0.82549 (5)	0.0360 (4)
O2	0.6965 (2)	0.6799 (2)	0.89410 (6)	0.0410 (4)
O3	0.3787 (2)	0.7650 (2)	0.98007 (5)	0.0361 (4)
H3O	0.249 (4)	0.769 (4)	1.0033 (10)	0.058 (7)*
C1	0.5252 (3)	0.7878 (3)	0.88106 (7)	0.0296 (5)
C2	0.3065 (3)	0.8247 (3)	0.92142 (7)	0.0272 (4)
H2	0.178 (3)	0.732 (3)	0.9067 (7)	0.028 (5)*
C3	0.2162 (3)	1.0476 (3)	0.91739 (7)	0.0256 (5)
H3	0.064 (3)	1.055 (3)	0.9395 (6)	0.021 (4)*
C4	0.1557 (3)	1.0900 (3)	0.85078 (8)	0.0262 (4)
H4	0.041 (3)	0.986 (3)	0.8395 (7)	0.024 (5)*
C5	0.3836 (3)	1.0619 (3)	0.81287 (8)	0.0330 (5)
H5A	0.338 (3)	1.055 (2)	0.7706 (8)	0.025 (4)*
H5B	0.502 (3)	1.182 (3)	0.8212 (7)	0.030 (5)*
C6	0.3998 (4)	1.1984 (4)	0.94473 (9)	0.0358 (5)
H6A	0.415 (3)	1.169 (3)	0.9876 (8)	0.033 (5)*
H6B	0.561 (4)	1.184 (3)	0.9246 (8)	0.046 (6)*
H6C	0.335 (4)	1.347 (4)	0.9409 (8)	0.050 (6)*
C7	0.0438 (3)	1.3007 (3)	0.84232 (8)	0.0297 (5)
H7	−0.073 (3)	1.337 (3)	0.8724 (7)	0.033 (5)*
C8	0.0979 (4)	1.4381 (3)	0.80057 (9)	0.0360 (5)
H8A	0.020 (3)	1.575 (3)	0.8003 (7)	0.034 (5)*
H8B	0.225 (4)	1.415 (3)	0.7692 (9)	0.050 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0363 (7)	0.0428 (9)	0.0288 (7)	0.0135 (7)	0.0068 (6)	0.0009 (6)
O2	0.0334 (8)	0.0448 (9)	0.0448 (8)	0.0126 (8)	0.0043 (6)	0.0038 (7)
O3	0.0334 (7)	0.0450 (10)	0.0300 (7)	0.0077 (7)	0.0038 (6)	0.0099 (7)
C1	0.0289 (10)	0.0290 (12)	0.0308 (10)	0.0010 (10)	−0.0019 (8)	−0.0027 (9)
C2	0.0262 (9)	0.0285 (11)	0.0269 (9)	0.0007 (9)	−0.0012 (8)	0.0017 (8)
C3	0.0218 (9)	0.0284 (12)	0.0267 (9)	−0.0006 (9)	0.0045 (8)	0.0006 (8)
C4	0.0231 (9)	0.0282 (12)	0.0274 (9)	0.0000 (9)	−0.0006 (8)	−0.0011 (9)
C5	0.0315 (11)	0.0398 (14)	0.0278 (10)	0.0082 (11)	−0.0002 (9)	0.0023 (10)
C6	0.0391 (12)	0.0372 (14)	0.0311 (11)	−0.0045 (11)	−0.0003 (9)	−0.0027 (10)
C7	0.0264 (10)	0.0348 (12)	0.0278 (9)	0.0028 (9)	0.0012 (8)	−0.0002 (9)
C8	0.0400 (12)	0.0348 (14)	0.0333 (11)	0.0043 (11)	−0.0018 (10)	0.0012 (11)

Geometric parameters (Å, º)

O1—C1	1.351 (2)	C4—C5	1.512 (3)
O1—C5	1.456 (2)	C4—H4	0.952 (18)
O2—C1	1.200 (2)	C5—H5A	0.973 (17)
O3—C2	1.415 (2)	C5—H5B	1.024 (19)
O3—H3O	0.88 (2)	C6—H6A	0.974 (18)
C1—C2	1.510 (2)	C6—H6B	0.99 (2)
C2—C3	1.522 (3)	C6—H6C	1.02 (2)
C2—H2	0.977 (19)	C7—C8	1.316 (3)
C3—C6	1.522 (3)	C7—H7	0.952 (18)
C3—C4	1.541 (2)	C8—H8A	0.98 (2)
C3—H3	0.964 (17)	C8—H8B	1.00 (2)
C4—C7	1.502 (3)
C1—O1—C5	121.78 (14)	C5—C4—H4	108.0 (10)
C2—O3—H3O	108.0 (14)	C3—C4—H4	105.5 (10)
O2—C1—O1	118.19 (16)	O1—C5—C4	114.33 (15)
O2—C1—C2	124.20 (16)	O1—C5—H5A	106.3 (10)
O1—C1—C2	117.49 (16)	C4—C5—H5A	109.5 (10)
O3—C2—C1	106.53 (14)	O1—C5—H5B	106.0 (9)
O3—C2—C3	113.67 (15)	C4—C5—H5B	109.2 (9)
C1—C2—C3	111.67 (16)	H5A—C5—H5B	111.6 (13)
O3—C2—H2	110.0 (10)	C3—C6—H6A	109.0 (11)
C1—C2—H2	105.7 (10)	C3—C6—H6B	110.2 (12)
C3—C2—H2	109.0 (10)	H6A—C6—H6B	110.3 (15)
C2—C3—C6	111.57 (15)	C3—C6—H6C	109.7 (12)
C2—C3—C4	107.06 (14)	H6A—C6—H6C	106.9 (16)
C6—C3—C4	114.26 (17)	H6B—C6—H6C	110.7 (19)
C2—C3—H3	107.0 (11)	C8—C7—C4	127.34 (18)
C6—C3—H3	109.4 (10)	C8—C7—H7	118.7 (12)
C4—C3—H3	107.2 (9)	C4—C7—H7	113.9 (12)
C7—C4—C5	111.85 (16)	C7—C8—H8A	120.9 (10)
C7—C4—C3	111.58 (15)	C7—C8—H8B	123.2 (13)
C5—C4—C3	109.76 (15)	H8A—C8—H8B	115.8 (17)
C7—C4—H4	109.9 (10)
C5—O1—C1—O2	−155.30 (18)	C2—C3—C4—C7	175.08 (14)
C5—O1—C1—C2	28.4 (2)	C6—C3—C4—C7	−60.9 (2)
O2—C1—C2—O3	17.4 (3)	C2—C3—C4—C5	−60.4 (2)
O1—C1—C2—O3	−166.52 (16)	C6—C3—C4—C5	63.7 (2)
O2—C1—C2—C3	142.05 (19)	C1—O1—C5—C4	−31.6 (3)
O1—C1—C2—C3	−41.9 (2)	C7—C4—C5—O1	171.65 (15)
O3—C2—C3—C6	52.0 (2)	C3—C4—C5—O1	47.2 (2)
C1—C2—C3—C6	−68.52 (19)	C5—C4—C7—C8	11.9 (3)
O3—C2—C3—C4	177.73 (15)	C3—C4—C7—C8	135.3 (2)
C1—C2—C3—C4	57.18 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O2^i	0.88 (2)	2.32 (2)	2.9881 (18)	133.0 (17)
O3—H3O···O3^i	0.88 (2)	2.06 (2)	2.8713 (8)	153.1 (19)

Symmetry code: (i) x−1/2, −y+3/2, −z+2.