(3R,4R,5S)-4-Hydr-oxy-3-methyl-5-[(2S,3R)-3-methyl-pent-4-en-2-yl]-4,5-dihydro-furan-2(3H)-one.

The relative configuration of the title compound, C(11)H(18)O(3), which was synthesized using a catalytic asymmetric Gosteli-Claisen rearrangement, a diastereoselective reduction with K-Selectride and an Evans aldol addition, was corroborated by single-crystal X-ray diffraction analysis. The five-membered ring has an envelope conformation with a dihedral angle of 29.46 (16)° between the coplanar part and the flap (the hydr-oxy-bearing ring C atom). In the crystal, mol-ecules are connected via bifurcated O-H⋯(O,O) hydrogen bonds, generating [010] chains.

Related literature

For further synthetic details, see: Abraham et al. (2001 ▶, 2004 ▶); Brown (1973 ▶); Evans et al. (1981 ▶, 1999 ▶); Otera et al. (1992 ▶). For the structure of the major diastereisomer arising from the same reaction, see: Gille et al. (2008 ▶).

Experimental

Crystal data

C11H18O3

M = 198.25

Monoclinic,

a = 7.7265 (10) Å

b = 6.4798 (8) Å

c = 11.0598 (16) Å

β = 92.563 (14)°

V = 553.17 (13) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 173 K

0.50 × 0.18 × 0.04 mm

Data collection

Oxford Diffraction Xcalibur S CCD diffractometer

Absorption correction: none

3255 measured reflections

1129 independent reflections

737 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.048

S = 0.99

1129 reflections

131 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.14 e Å−3

Δρmin = −0.15 e Å−3

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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050399/hb5238sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809050399/hb5238Isup2.hkl

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

C11H18O3	F(000) = 216
Mr = 198.25	Dx = 1.190 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1159 reflections
a = 7.7265 (10) Å	θ = 2.6–29.1°
b = 6.4798 (8) Å	µ = 0.09 mm−1
c = 11.0598 (16) Å	T = 173 K
β = 92.563 (14)°	Plate, colourless
V = 553.17 (13) Å3	0.50 × 0.18 × 0.04 mm
Z = 2

Oxford Diffraction Xcalibur S CCD diffractometer	737 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.040
graphite	θmax = 25.5°, θmin = 2.6°
Detector resolution: 16.0560 pixels mm-1	h = −10→10
ω scans	k = −7→8
3255 measured reflections	l = −14→14
1129 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.048	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.011P)2] where P = (Fo2 + 2Fc2)/3
1129 reflections	(Δ/σ)max < 0.001
131 parameters	Δρmax = 0.14 e Å−3
1 restraint	Δρmin = −0.15 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.2173 (2)	0.1438 (2)	0.07628 (15)	0.0251 (5)
O2	0.2731 (2)	0.0175 (3)	−0.10413 (17)	0.0328 (6)
O3	0.1599 (2)	0.6838 (3)	0.05289 (17)	0.0370 (6)
H3	0.2032	0.7730	0.0082	0.056*
C1	0.2453 (3)	0.1658 (5)	−0.0428 (2)	0.0267 (8)
C2	0.2329 (4)	0.3900 (4)	−0.0771 (2)	0.0251 (8)
H2	0.1128	0.4168	−0.1109	0.030*
C3	0.2533 (3)	0.4969 (4)	0.0446 (2)	0.0275 (8)
H3A	0.3790	0.5230	0.0645	0.033*
C4	0.1847 (4)	0.3431 (4)	0.1331 (3)	0.0251 (7)
H4	0.0569	0.3630	0.1382	0.030*
C5	0.2674 (4)	0.3375 (4)	0.2598 (2)	0.0293 (8)
H5	0.3954	0.3280	0.2512	0.035*
C6	0.2135 (4)	0.1458 (4)	0.3322 (2)	0.0314 (8)
H6	0.2292	0.0238	0.2784	0.038*
C7	0.3345 (4)	0.1158 (5)	0.4405 (3)	0.0409 (9)
H7	0.4546	0.1147	0.4255	0.049*
C8	0.2950 (4)	0.0912 (5)	0.5523 (2)	0.0487 (10)
H8A	0.1770	0.0910	0.5730	0.058*
H8B	0.3841	0.0735	0.6134	0.058*
C9	0.3607 (3)	0.4531 (4)	−0.1730 (2)	0.0350 (9)
H9A	0.4789	0.4182	−0.1443	0.053*
H9B	0.3523	0.6022	−0.1872	0.053*
H9C	0.3323	0.3793	−0.2487	0.053*
C10	0.2329 (4)	0.5418 (4)	0.3243 (2)	0.0401 (9)
H10A	0.2922	0.6541	0.2836	0.060*
H10B	0.2765	0.5329	0.4087	0.060*
H10C	0.1080	0.5689	0.3218	0.060*
C11	0.0231 (3)	0.1493 (5)	0.3622 (2)	0.0434 (9)
H11A	−0.0082	0.0167	0.3979	0.065*
H11B	−0.0484	0.1728	0.2881	0.065*
H11C	0.0033	0.2605	0.4201	0.065*

	U11	U22	U33	U12	U13	U23
O1	0.0324 (13)	0.0134 (13)	0.0295 (11)	−0.0005 (11)	0.0026 (10)	−0.0004 (11)
O2	0.0385 (14)	0.0195 (12)	0.0403 (14)	−0.0003 (11)	0.0013 (11)	−0.0058 (12)
O3	0.0427 (14)	0.0116 (11)	0.0573 (15)	0.0053 (11)	0.0087 (11)	0.0052 (12)
C1	0.0145 (16)	0.0214 (18)	0.044 (2)	−0.0032 (17)	−0.0048 (15)	0.003 (2)
C2	0.0219 (17)	0.0155 (18)	0.038 (2)	−0.0004 (14)	0.0015 (15)	0.0037 (15)
C3	0.0222 (18)	0.0125 (16)	0.048 (2)	0.0004 (16)	0.0007 (16)	0.0048 (16)
C4	0.0229 (17)	0.0143 (16)	0.0380 (19)	0.0038 (15)	0.0020 (15)	−0.0005 (16)
C5	0.0261 (17)	0.0224 (19)	0.039 (2)	0.0040 (16)	−0.0001 (16)	−0.0068 (17)
C6	0.048 (2)	0.0133 (19)	0.0330 (18)	0.0029 (17)	0.0011 (16)	−0.0060 (17)
C7	0.049 (2)	0.038 (2)	0.0359 (17)	0.0078 (19)	0.0001 (17)	0.0032 (18)
C8	0.054 (3)	0.052 (2)	0.039 (2)	−0.003 (2)	−0.005 (2)	0.0019 (19)
C9	0.0337 (19)	0.0271 (19)	0.045 (2)	−0.0014 (17)	0.0090 (16)	0.0070 (17)
C10	0.046 (2)	0.025 (2)	0.049 (2)	−0.0045 (17)	0.0060 (18)	−0.0113 (17)
C11	0.049 (2)	0.037 (2)	0.0442 (19)	−0.010 (2)	0.0005 (17)	0.007 (2)

O1—C1	1.352 (3)	C6—C7	1.499 (3)
O1—C4	1.463 (3)	C6—C11	1.523 (3)
O2—C1	1.201 (3)	C6—H6	1.0000
O3—C3	1.415 (3)	C7—C8	1.296 (3)
O3—H3	0.8400	C7—H7	0.9500
C1—C2	1.504 (4)	C8—H8A	0.9500
C2—C3	1.516 (3)	C8—H8B	0.9500
C2—C9	1.536 (3)	C9—H9A	0.9800
C2—H2	1.0000	C9—H9B	0.9800
C3—C4	1.510 (3)	C9—H9C	0.9800
C3—H3A	1.0000	C10—H10A	0.9800
C4—C5	1.515 (3)	C10—H10B	0.9800
C4—H4	1.0000	C10—H10C	0.9800
C5—C10	1.533 (3)	C11—H11A	0.9800
C5—C6	1.544 (4)	C11—H11B	0.9800
C5—H5	1.0000	C11—H11C	0.9800
C1—O1—C4	111.3 (2)	C7—C6—C5	110.2 (2)
C3—O3—H3	109.5	C11—C6—C5	112.7 (2)
O2—C1—O1	120.4 (3)	C7—C6—H6	106.6
O2—C1—C2	129.9 (2)	C11—C6—H6	106.6
O1—C1—C2	109.7 (3)	C5—C6—H6	106.6
C1—C2—C3	102.4 (2)	C8—C7—C6	127.8 (3)
C1—C2—C9	113.4 (2)	C8—C7—H7	116.1
C3—C2—C9	116.5 (2)	C6—C7—H7	116.1
C1—C2—H2	108.1	C7—C8—H8A	120.0
C3—C2—H2	108.1	C7—C8—H8B	120.0
C9—C2—H2	108.1	H8A—C8—H8B	120.0
O3—C3—C4	109.1 (2)	C2—C9—H9A	109.5
O3—C3—C2	114.6 (2)	C2—C9—H9B	109.5
C4—C3—C2	104.4 (2)	H9A—C9—H9B	109.5
O3—C3—H3A	109.5	C2—C9—H9C	109.5
C4—C3—H3A	109.5	H9A—C9—H9C	109.5
C2—C3—H3A	109.5	H9B—C9—H9C	109.5
O1—C4—C3	103.4 (2)	C5—C10—H10A	109.5
O1—C4—C5	107.6 (2)	C5—C10—H10B	109.5
C3—C4—C5	118.0 (2)	H10A—C10—H10B	109.5
O1—C4—H4	109.1	C5—C10—H10C	109.5
C3—C4—H4	109.1	H10A—C10—H10C	109.5
C5—C4—H4	109.1	H10B—C10—H10C	109.5
C4—C5—C10	109.6 (2)	C6—C11—H11A	109.5
C4—C5—C6	112.7 (2)	C6—C11—H11B	109.5
C10—C5—C6	113.4 (2)	H11A—C11—H11B	109.5
C4—C5—H5	106.9	C6—C11—H11C	109.5
C10—C5—H5	106.9	H11A—C11—H11C	109.5
C6—C5—H5	106.9	H11B—C11—H11C	109.5
C7—C6—C11	113.6 (2)
C4—O1—C1—O2	−179.5 (2)	C2—C3—C4—O1	28.3 (3)
C4—O1—C1—C2	−0.1 (3)	O3—C3—C4—C5	−90.1 (3)
O2—C1—C2—C3	−162.7 (3)	C2—C3—C4—C5	147.0 (2)
O1—C1—C2—C3	18.0 (3)	O1—C4—C5—C10	−178.7 (2)
O2—C1—C2—C9	−36.3 (4)	C3—C4—C5—C10	64.9 (3)
O1—C1—C2—C9	144.4 (2)	O1—C4—C5—C6	−51.4 (3)
C1—C2—C3—O3	−147.4 (2)	C3—C4—C5—C6	−167.8 (2)
C9—C2—C3—O3	88.3 (3)	C4—C5—C6—C7	163.9 (2)
C1—C2—C3—C4	−28.1 (3)	C10—C5—C6—C7	−70.9 (3)
C9—C2—C3—C4	−152.4 (2)	C4—C5—C6—C11	−68.0 (3)
C1—O1—C4—C3	−18.0 (3)	C10—C5—C6—C11	57.3 (3)
C1—O1—C4—C5	−143.6 (2)	C11—C6—C7—C8	0.8 (5)
O3—C3—C4—O1	151.2 (2)	C5—C6—C7—C8	128.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1i	0.84	2.52	3.023 (2)	120
O3—H3···O2i	0.84	2.10	2.931 (3)	171

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1i	0.84	2.52	3.023 (2)	120
O3—H3⋯O2i	0.84	2.10	2.931 (3)	171

Symmetry code: (i) .