(+)-(1S,5R,10S)-11,11-Dimeth-yl-4-oxa-tricyclo-[8.4.0.0]tetra-deca-ne-3,12-dione.

The title compound, C(15)H(22)O(3), was prepared via amino-acid-promoted Robinson annulation followed by tandem Pd/C-mediated hydrogenation and oxidative cyclization. This product was instrumental in determining the feasibility of a stereocontrolled hydrogenation in which the directing hydroxyl group is adjacent to the 6-7-ring network and its olefinic component. The asymmetric unit consists of a single mol-ecule with normal geometric parameters. The absolute configuration was assigned based on the known enanti-omeric prescursor. Inter-molecular C-H⋯O inter-actions link each mol-ecule with four neighboring mol-ecules.

Related literature

For related chemistry, see: Brown (1987 ▶); Crabtree & Davis (1986 ▶); Inomata et al. (2005 ▶), Nagamine et al. (2007 ▶); Peng et al. (2004 ▶); Stork & Kahne (1983 ▶). For related literature on geometry, see: Allen et al. (1987 ▶); Desiraju & Steiner (1999 ▶); Steiner & Saenger (1992 ▶); Taylor & Kennard (1982 ▶).

Experimental

Crystal data

C15H22O3

M = 250.33

Trigonal,

a = 7.6239 (10) Å

c = 38.064 (5) Å

V = 1916.0 (4) Å3

Z = 6

Mo Kα radiation

μ = 0.09 mm−1

T = 150 (2) K

0.35 × 0.27 × 0.19 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: none

23396 measured reflections

1130 independent reflections

1023 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.057

S = 1.06

1130 reflections

165 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.11 e Å−3

Δρmin = −0.14 e Å−3

Data collection: COLLECT (Nonius, 1997–2000 ▶); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997 ▶); data reduction: HKL DENZO (Otwinowski & Minor 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and SHELXTL (Bruker, 1999 ▶); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807066159/sq2007sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807066159/sq2007Isup2.hkl

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

C15H22O3	Z = 6
Mr = 250.33	F000 = 816
Trigonal, P65	Dx = 1.302 Mg m−3
Hall symbol: P 65	Mo Kα radiation λ = 0.71073 Å
a = 7.6239 (10) Å	Cell parameters from 2164 reflections
b = 7.6239 (10) Å	θ = 2.0–25.0º
c = 38.064 (5) Å	µ = 0.09 mm−1
α = 90º	T = 150 (2) K
β = 90º	Chunk, colorless
γ = 120º	0.35 × 0.27 × 0.19 mm
V = 1916.0 (4) Å3

Nonius KappaCCD diffractometer	1023 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.038
Detector resolution: 9 pixels mm-1	θmax = 25.0º
T = 150(2) K	θmin = 3.1º
ω scans	h = −9→9
Absorption correction: none	k = −7→7
23396 measured reflections	l = −44→44
1130 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026	H-atom parameters constrained
wR(F2) = 0.057	w = 1/[σ2(Fo2) + (0.0353P)2 + 0.1114P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
1130 reflections	Δρmax = 0.11 e Å−3
165 parameters	Δρmin = −0.14 e Å−3
1 restraint	Extinction correction: none
Primary atom site location: structure-invariant direct methods

Experimental. The data collection crystal was a clear, colorless chunk, which was cut from a cluster of crystals. Initial examination of the diffraction pattern on a Nonius Kappa CCD diffractometer indicated a trigonal or hexagonal crystal system. All work was done at 150 K using an Oxford Cryosystems Cryostream Cooler. Omega scans with a frame width of 1.0 degree were used for data collection. Data integration was done with DENZO (Otwinowski & Minor, 1997) and scaling and merging of the data was done with SCALEPACK (Otwinowski & Minor, 1997).The Laue group was determined to be 6/m by XPREP (Bruker Nonius, 2003). The intensity statistics are non-centrosymmetric and the systematic absences restrict the space group possibilities to P61 or P65. The structure was solved by the direct methods procedure in SHELXS86 (Sheldrick, 1990). Full-matrix least-squares refinements based on F2 were performed in SHELXL97 (Sheldrick, 1997), as incorporated in the WinGX package (Farrugia, 1999). The correct enantiomer was chosen based on the known chiral centers at atoms C(1) and C(5).

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
C1	1.1237 (3)	0.6294 (3)	0.84987 (5)	0.0200 (4)
C2	0.9527 (3)	0.4864 (3)	0.87492 (5)	0.0248 (5)
H2A	0.8387	0.5136	0.8738	0.03*
H2B	0.9017	0.3435	0.8682	0.03*
C3	1.0397 (3)	0.5250 (3)	0.91134 (5)	0.0245 (5)
C5	1.3134 (3)	0.7149 (3)	0.87446 (5)	0.0236 (4)
H5	1.3852	0.6387	0.8688	0.028*
C6	1.4721 (3)	0.9388 (3)	0.87398 (6)	0.0273 (5)
H6A	1.5073	0.9816	0.8492	0.033*
H6B	1.5958	0.956	0.8856	0.033*
C7	1.4117 (3)	1.0810 (3)	0.89168 (6)	0.0276 (5)
H7A	1.3505	1.023	0.9148	0.033*
H7B	1.536	1.2123	0.8961	0.033*
C8	1.2636 (3)	1.1208 (3)	0.87107 (5)	0.0266 (5)
H8A	1.3305	1.1937	0.8492	0.032*
H8B	1.2318	1.2105	0.8851	0.032*
C9	1.0656 (3)	0.9300 (3)	0.86149 (5)	0.0234 (5)
H9A	0.9685	0.9697	0.8525	0.028*
H9B	1.0067	0.8479	0.883	0.028*
C10	1.0931 (3)	0.7992 (3)	0.83360 (5)	0.0196 (4)
H10	1.2246	0.8928	0.8218	0.024*
C11	0.9294 (3)	0.7288 (3)	0.80369 (5)	0.0204 (4)
C12	0.9724 (3)	0.6034 (3)	0.77757 (5)	0.0207 (4)
C13	0.9882 (3)	0.4299 (3)	0.79298 (5)	0.0243 (5)
H13A	1.0177	0.3585	0.7742	0.029*
H13B	0.8586	0.3322	0.8043	0.029*
C14	1.1584 (3)	0.5144 (3)	0.82012 (5)	0.0235 (5)
H14A	1.2879	0.6068	0.8082	0.028*
H14B	1.1702	0.4012	0.8303	0.028*
C15	0.9500 (3)	0.9168 (3)	0.78510 (6)	0.0289 (5)
H15A	0.8683	0.8756	0.7636	0.043*
H15B	1.0924	1.0085	0.7791	0.043*
H15C	0.9024	0.9865	0.8007	0.043*
C16	0.7081 (3)	0.5997 (3)	0.81654 (6)	0.0280 (5)
H16A	0.6841	0.4669	0.8243	0.042*
H16B	0.6153	0.582	0.7973	0.042*
H16C	0.6847	0.6685	0.8362	0.042*
O1	0.9541 (2)	0.4526 (2)	0.93853 (4)	0.0347 (4)
O2	1.0008 (2)	0.6444 (2)	0.74647 (4)	0.0259 (3)
O4	1.2389 (2)	0.6617 (2)	0.91052 (3)	0.0268 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0192 (11)	0.0211 (10)	0.0205 (10)	0.0106 (9)	0.0003 (8)	0.0024 (8)
C2	0.0243 (11)	0.0238 (11)	0.0249 (12)	0.0110 (9)	0.0024 (9)	0.0042 (9)
C3	0.0293 (11)	0.0244 (11)	0.0253 (12)	0.0176 (9)	0.0048 (10)	0.0057 (9)
C5	0.0249 (11)	0.0296 (11)	0.0183 (10)	0.0152 (9)	0.0027 (8)	0.0048 (9)
C6	0.0189 (10)	0.0322 (12)	0.0288 (12)	0.0113 (10)	−0.0025 (9)	0.0015 (9)
C7	0.0230 (11)	0.0247 (11)	0.0277 (12)	0.0063 (9)	−0.0020 (9)	−0.0001 (9)
C8	0.0309 (12)	0.0228 (11)	0.0241 (11)	0.0119 (9)	−0.0014 (9)	−0.0025 (9)
C9	0.0267 (11)	0.0262 (11)	0.0205 (11)	0.0157 (9)	0.0013 (9)	0.0002 (9)
C10	0.0182 (10)	0.0204 (10)	0.0199 (10)	0.0095 (8)	0.0012 (8)	0.0022 (8)
C11	0.0213 (10)	0.0243 (10)	0.0181 (10)	0.0132 (9)	0.0003 (8)	0.0008 (8)
C12	0.0139 (9)	0.0225 (11)	0.0218 (11)	0.0061 (9)	−0.0036 (8)	−0.0017 (8)
C13	0.0282 (11)	0.0238 (11)	0.0230 (11)	0.0145 (9)	0.0017 (9)	−0.0030 (9)
C14	0.0266 (11)	0.0232 (10)	0.0247 (11)	0.0155 (9)	0.0024 (9)	0.0037 (9)
C15	0.0376 (13)	0.0335 (11)	0.0235 (11)	0.0236 (10)	−0.0037 (9)	−0.0009 (9)
C16	0.0211 (11)	0.0372 (12)	0.0261 (12)	0.0149 (9)	−0.0028 (9)	−0.0034 (9)
O1	0.0416 (9)	0.0421 (9)	0.0235 (9)	0.0231 (8)	0.0099 (7)	0.0100 (7)
O2	0.0265 (8)	0.0292 (8)	0.0196 (8)	0.0120 (7)	−0.0007 (6)	−0.0011 (6)
O4	0.0269 (8)	0.0324 (8)	0.0193 (7)	0.0135 (7)	0.0000 (6)	0.0046 (6)

C1—C14	1.534 (3)	C9—C10	1.541 (3)
C1—C2	1.542 (3)	C9—H9A	0.99
C1—C10	1.554 (3)	C9—H9B	0.99
C1—C5	1.565 (3)	C10—C11	1.573 (3)
C2—C3	1.501 (3)	C10—H10	1
C2—H2A	0.99	C11—C12	1.524 (3)
C2—H2B	0.99	C11—C15	1.534 (3)
C3—O1	1.201 (2)	C11—C16	1.547 (3)
C3—O4	1.345 (2)	C12—O2	1.216 (2)
C5—O4	1.463 (2)	C12—C13	1.505 (3)
C5—C6	1.521 (3)	C13—C14	1.527 (3)
C5—H5	1	C13—H13A	0.99
C6—C7	1.530 (3)	C13—H13B	0.99
C6—H6A	0.99	C14—H14A	0.99
C6—H6B	0.99	C14—H14B	0.99
C7—C8	1.524 (3)	C15—H15A	0.98
C7—H7A	0.99	C15—H15B	0.98
C7—H7B	0.99	C15—H15C	0.98
C8—C9	1.527 (3)	C16—H16A	0.98
C8—H8A	0.99	C16—H16B	0.98
C8—H8B	0.99	C16—H16C	0.98
C14—C1—C2	112.26 (16)	C10—C9—H9B	109
C14—C1—C10	108.82 (16)	H9A—C9—H9B	107.8
C2—C1—C10	114.16 (16)	C9—C10—C1	112.96 (15)
C14—C1—C5	106.98 (16)	C9—C10—C11	112.20 (15)
C2—C1—C5	101.73 (15)	C1—C10—C11	115.38 (15)
C10—C1—C5	112.57 (16)	C9—C10—H10	105
C3—C2—C1	107.32 (16)	C1—C10—H10	105
C3—C2—H2A	110.3	C11—C10—H10	105
C1—C2—H2A	110.3	C12—C11—C15	109.38 (15)
C3—C2—H2B	110.3	C12—C11—C16	108.37 (16)
C1—C2—H2B	110.3	C15—C11—C16	108.06 (16)
H2A—C2—H2B	108.5	C12—C11—C10	107.64 (14)
O1—C3—O4	121.31 (18)	C15—C11—C10	108.80 (15)
O1—C3—C2	128.34 (18)	C16—C11—C10	114.52 (16)
O4—C3—C2	110.34 (16)	O2—C12—C13	121.53 (18)
O4—C5—C6	107.62 (16)	O2—C12—C11	122.68 (17)
O4—C5—C1	107.19 (15)	C13—C12—C11	115.72 (16)
C6—C5—C1	120.72 (16)	C12—C13—C14	108.53 (16)
O4—C5—H5	106.9	C12—C13—H13A	110
C6—C5—H5	106.9	C14—C13—H13A	110
C1—C5—H5	106.9	C12—C13—H13B	110
C5—C6—C7	115.98 (17)	C14—C13—H13B	110
C5—C6—H6A	108.3	H13A—C13—H13B	108.4
C7—C6—H6A	108.3	C13—C14—C1	112.81 (15)
C5—C6—H6B	108.3	C13—C14—H14A	109
C7—C6—H6B	108.3	C1—C14—H14A	109
H6A—C6—H6B	107.4	C13—C14—H14B	109
C8—C7—C6	115.44 (17)	C1—C14—H14B	109
C8—C7—H7A	108.4	H14A—C14—H14B	107.8
C6—C7—H7A	108.4	C11—C15—H15A	109.5
C8—C7—H7B	108.4	C11—C15—H15B	109.5
C6—C7—H7B	108.4	H15A—C15—H15B	109.5
H7A—C7—H7B	107.5	C11—C15—H15C	109.5
C7—C8—C9	114.27 (17)	H15A—C15—H15C	109.5
C7—C8—H8A	108.7	H15B—C15—H15C	109.5
C9—C8—H8A	108.7	C11—C16—H16A	109.5
C7—C8—H8B	108.7	C11—C16—H16B	109.5
C9—C8—H8B	108.7	H16A—C16—H16B	109.5
H8A—C8—H8B	107.6	C11—C16—H16C	109.5
C8—C9—C10	113.03 (17)	H16A—C16—H16C	109.5
C8—C9—H9A	109	H16B—C16—H16C	109.5
C10—C9—H9A	109	C3—O4—C5	111.59 (15)
C8—C9—H9B	109
C14—C1—C2—C3	124.11 (17)	C5—C1—C10—C11	169.82 (15)
C10—C1—C2—C3	−111.44 (18)	C9—C10—C11—C12	179.42 (16)
C5—C1—C2—C3	10.1 (2)	C1—C10—C11—C12	−49.3 (2)
C1—C2—C3—O1	175.8 (2)	C9—C10—C11—C15	61.0 (2)
C1—C2—C3—O4	−3.3 (2)	C1—C10—C11—C15	−167.71 (16)
C14—C1—C5—O4	−131.22 (17)	C9—C10—C11—C16	−60.0 (2)
C2—C1—C5—O4	−13.32 (19)	C1—C10—C11—C16	71.3 (2)
C10—C1—C5—O4	109.29 (17)	C15—C11—C12—O2	−5.6 (2)
C14—C1—C5—C6	105.2 (2)	C16—C11—C12—O2	112.0 (2)
C2—C1—C5—C6	−136.86 (18)	C10—C11—C12—O2	−123.67 (19)
C10—C1—C5—C6	−14.2 (3)	C15—C11—C12—C13	171.40 (17)
O4—C5—C6—C7	−49.0 (2)	C16—C11—C12—C13	−71.0 (2)
C1—C5—C6—C7	74.4 (2)	C10—C11—C12—C13	53.3 (2)
C5—C6—C7—C8	−74.9 (2)	O2—C12—C13—C14	118.03 (19)
C6—C7—C8—C9	56.7 (2)	C11—C12—C13—C14	−59.0 (2)
C7—C8—C9—C10	−69.9 (2)	C12—C13—C14—C1	59.0 (2)
C8—C9—C10—C1	93.9 (2)	C2—C1—C14—C13	71.8 (2)
C8—C9—C10—C11	−133.64 (17)	C10—C1—C14—C13	−55.6 (2)
C14—C1—C10—C9	−177.66 (16)	C5—C1—C14—C13	−177.43 (16)
C2—C1—C10—C9	56.1 (2)	O1—C3—O4—C5	174.92 (18)
C5—C1—C10—C9	−59.3 (2)	C2—C3—O4—C5	−5.8 (2)
C14—C1—C10—C11	51.4 (2)	C6—C5—O4—C3	143.75 (16)
C2—C1—C10—C11	−74.9 (2)	C1—C5—O4—C3	12.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1i	1	2.70	3.596 (2)	149
C14—H14A···O1i	0.99	2.70	3.562 (3)	146
C2—H2A···O2ii	0.99	2.62	3.449 (2)	141
C9—H9B···O2ii	0.99	2.66	3.454 (2)	138
C5—H5···O2iii	1	2.58	3.194 (2)	119

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O1i	1.00	2.70	3.596 (2)	149
C14—H14A⋯O1i	0.99	2.70	3.562 (3)	146
C2—H2A⋯O2ii	0.99	2.62	3.449 (2)	141
C9—H9B⋯O2ii	0.99	2.66	3.454 (2)	138
C5—H5⋯O2iii	1.00	2.58	3.194 (2)	119

Symmetry codes: (i) ; (ii) ; (iii) .