(5S*,6R*)-1,7-Dioxa­di­spiro­[4.0.4.4]­tetra­decane-2,8-dione

The title compound, C₁₂H₁₆O₄, (I), was prepared by oxidation of (5S*,6R*)-1,7-di­oxa­di­spiro­[4.0.4.4]­tetra­decane-2,8-diol us­ing silver(I) carbonate and posesses a cis configuration of the two five-membered-ring lactones fused spiro to the six-membered carbocycle, which has a chair conformation. It represents an exceptional structure for bis-tetra­hydro­furan units, which are interesting building blocks in natural products. The synthesis, spectroscopic data and X-ray structural analysis are described. The crystal contains discrete mol­ecules separated by normal van der Waals distances.

S1. Comment

NOT REQUIRED

S2. Experimental

Following the procedure of Nozaki et al. (1997) (5S*,6R*)-1,7-dioxadispiro[4.0.4.4]tetradecane-2,8-diol (300 mg, 1.31 mmol) and silver(I) carbonate (1.65 g, 5.98 mmol) in dry benzene (15 ml) were heated under reflux for 30 h. After cooling to room temperature, 2.5 g of celite was added and the mixture was stirred for an additional 10 min. The solid was filtered off and washed with methyl tert-butyl ether. After evaporation of the solvent, the crude product (light-yellow crystals, 260 mg) was recrystallized from 20 ml diethyl ether to give 212 mg (0.95 mmol, 72%) (5S*,6R*)-1,7-dioxadispiro[4.0.4.4]tetradecane-2,8-dione as colourless crystals. Analysis calculated for C₁₂H₁₆O₄ (224.25 g mol⁻¹): C 64.27, H 7.19%; found: C 64.2, H 7.2%; MS (EI, 70 eV): m/z (%) = 224 (M+, 16), 206 (15), 178 (12), 162 (5), 150 (4), 124 (100), 111 (71), 96 (27), 83 (19), 67 (13), 55 (45); IR (KBr) ~v [cm⁻¹] = 2954 (s), 2940 (s), 2881 (m), 2863 (s), 1770 (versus), 1448 (m), 1280 (s), 1251 (s), 1193 (s), 1128 (s), 1035 (s), 983 (s), 925 (s); ¹H NMR (400 MHz, DMSO-d₆): δ (p.p.m.) = 1.46–1.76 (m, 6H), 1.87–1.95 (m, 2H), 2.00–2.18 (m, 4H), 2.50–2.61 (m, 2H), 2.71–2.81 (m, 2H); ¹³C NMR (100 MHz, dmso-d₆): δ (p.p.m.) = 20.96 (CH₂), 26.43 (CH₂), 28.06 (CH₂), 33.00 (CH₂), 87.80 (Cq), 176.02 (Cq, C═O); m.p.: 394 K.

S3. Refinement

All H atoms were located in a Δ-map and refined isotropically [C—H 0.917 (15)–1.023 (15) Å].

Computing details

Data collection: COLLECT Software (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995).

(I)

Crystal data

C12H16O4	F(000) = 480
Mr = 224.25	Dx = 1.351 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.8821 (2) Å	Cell parameters from 9511 reflections
b = 13.4754 (4) Å	θ = 3.4–27.5°
c = 12.0807 (4) Å	µ = 0.10 mm^−1
β = 100.3383 (19)°	T = 291 K
V = 1102.16 (6) Å^3	Block, colourless
Z = 4	0.40 × 0.39 × 0.26 mm

Data collection

Nonius KappaCCD diffractometer	1552 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 27.5°, θmin = 3.4°
Detector resolution: 10 vertical, 18 horizontal pixels mm^-1	h = −8→8
281 frames via ω–rotation (Δω=1°) and two times 20 s per frame with three sets at different κ angles scans	k = −17→17
9511 measured reflections	l = −15→15
2492 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	All H-atom parameters refined
wR(F^2) = 0.101	Calculated w = 1/[σ^2(Fo^2) + (0.0627P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.95	(Δ/σ)max < 0.001
2492 reflections	Δρmax = 0.16 e Å^−3
210 parameters	Δρmin = −0.15 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.035 (6)

Special details

Experimental. The data collection covered almost the whole sphere of reciprocal space. The crystal-to-detector distance was 3.4 cm. Crystal decay was monitored by repeating the initial frames at the end of the data collection and analysing the duplicate reflections there was no indication for any decay.

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	−0.10929 (13)	0.25692 (6)	0.66256 (8)	0.0509 (3)
O2	−0.31510 (15)	0.20079 (7)	0.51315 (9)	0.0689 (3)
O3	0.19961 (12)	0.24056 (6)	0.83872 (7)	0.0446 (3)
O4	0.33557 (14)	0.09793 (6)	0.90372 (9)	0.0620 (3)
C1	0.00572 (16)	0.34628 (8)	0.69944 (10)	0.0384 (3)
C2	−0.0937 (2)	0.39840 (11)	0.78622 (13)	0.0516 (4)
H2A	−0.224 (2)	0.4212 (10)	0.7474 (12)	0.059 (4)*
H2B	−0.1144 (19)	0.3491 (11)	0.8424 (12)	0.060 (4)*
C3	0.0278 (2)	0.48509 (12)	0.84106 (14)	0.0617 (4)
H3A	0.031 (2)	0.5369 (12)	0.7847 (14)	0.070 (4)*
H3B	−0.039 (2)	0.5153 (12)	0.8983 (15)	0.084 (5)*
C4	0.2356 (3)	0.45213 (12)	0.89227 (13)	0.0629 (4)
H4A	0.315 (2)	0.5066 (12)	0.9262 (14)	0.074 (5)*
H4B	0.224 (2)	0.4045 (10)	0.9567 (13)	0.062 (4)*
C5	0.3339 (2)	0.40130 (10)	0.80545 (13)	0.0511 (4)
H5A	0.3528 (19)	0.4472 (9)	0.7453 (12)	0.052 (4)*
H5B	0.468 (2)	0.3776 (9)	0.8385 (12)	0.061 (4)*
C6	0.21556 (16)	0.31332 (8)	0.74988 (10)	0.0389 (3)
C7	−0.20784 (19)	0.26578 (9)	0.55622 (12)	0.0480 (3)
C8	−0.1633 (2)	0.36326 (12)	0.50787 (14)	0.0581 (4)
H8A	−0.284 (3)	0.4032 (12)	0.4994 (14)	0.087 (5)*
H8B	−0.132 (2)	0.3510 (13)	0.4375 (16)	0.082 (5)*
C9	−0.0009 (2)	0.40806 (10)	0.59203 (11)	0.0420 (3)
H9A	−0.0224 (19)	0.4732 (11)	0.6083 (12)	0.057 (4)*
H9B	0.121 (2)	0.4062 (9)	0.5663 (12)	0.058 (4)*
C10	0.32307 (17)	0.16367 (9)	0.83560 (11)	0.0457 (3)
C11	0.4316 (2)	0.17563 (12)	0.73980 (15)	0.0608 (4)
H11A	0.437 (3)	0.1136 (14)	0.7016 (16)	0.091 (6)*
H11B	0.564 (3)	0.1968 (12)	0.7728 (16)	0.089 (6)*
C12	0.3215 (2)	0.25662 (11)	0.66823 (13)	0.0535 (4)
H12A	0.400 (2)	0.2985 (11)	0.6353 (12)	0.060 (4)*
H12B	0.228 (3)	0.2252 (11)	0.6070 (15)	0.074 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0522 (5)	0.0446 (5)	0.0527 (6)	−0.0111 (4)	0.0009 (4)	0.0083 (4)
O2	0.0677 (7)	0.0631 (6)	0.0724 (7)	−0.0175 (5)	0.0026 (5)	−0.0156 (5)
O3	0.0476 (5)	0.0467 (5)	0.0408 (5)	0.0057 (4)	0.0115 (4)	0.0123 (4)
O4	0.0637 (6)	0.0494 (6)	0.0707 (7)	0.0016 (4)	0.0065 (5)	0.0220 (5)
C1	0.0389 (6)	0.0360 (6)	0.0405 (7)	−0.0040 (5)	0.0079 (5)	0.0042 (5)
C2	0.0484 (8)	0.0589 (9)	0.0509 (9)	0.0108 (6)	0.0183 (7)	0.0106 (7)
C3	0.0805 (11)	0.0570 (9)	0.0484 (9)	0.0164 (8)	0.0136 (8)	−0.0062 (8)
C4	0.0807 (11)	0.0529 (9)	0.0501 (10)	−0.0041 (8)	−0.0015 (8)	−0.0057 (8)
C5	0.0463 (8)	0.0513 (8)	0.0526 (9)	−0.0045 (6)	0.0010 (7)	0.0093 (7)
C6	0.0408 (7)	0.0400 (6)	0.0373 (7)	0.0017 (5)	0.0111 (5)	0.0086 (5)
C7	0.0443 (7)	0.0509 (8)	0.0482 (8)	−0.0006 (6)	0.0068 (6)	−0.0052 (7)
C8	0.0643 (10)	0.0604 (9)	0.0462 (9)	−0.0094 (7)	0.0008 (7)	0.0070 (7)
C9	0.0449 (7)	0.0408 (8)	0.0399 (8)	0.0015 (6)	0.0067 (6)	0.0066 (6)
C10	0.0424 (7)	0.0415 (7)	0.0512 (8)	−0.0005 (5)	0.0025 (6)	0.0066 (7)
C11	0.0604 (10)	0.0585 (9)	0.0673 (10)	0.0176 (7)	0.0219 (8)	0.0116 (8)
C12	0.0551 (8)	0.0572 (8)	0.0520 (9)	0.0133 (7)	0.0202 (7)	0.0086 (7)

Geometric parameters (Å, º)

O1—C7	1.3461 (17)	C4—H4B	1.023 (15)
O1—C1	1.4657 (14)	C5—C6	1.5240 (17)
O2—C7	1.2020 (15)	C5—H5A	0.980 (14)
O3—C10	1.3447 (15)	C5—H5B	0.992 (15)
O3—C6	1.4723 (13)	C6—C12	1.5319 (17)
O4—C10	1.2016 (14)	C7—C8	1.492 (2)
C1—C2	1.5222 (18)	C8—C9	1.496 (2)
C1—C6	1.5291 (16)	C8—H8A	0.982 (18)
C1—C9	1.5355 (17)	C8—H8B	0.929 (18)
C2—C3	1.518 (2)	C9—H9A	0.917 (15)
C2—H2A	0.986 (14)	C9—H9B	0.943 (15)
C2—H2B	0.978 (15)	C10—C11	1.4945 (19)
C3—C4	1.519 (2)	C11—C12	1.509 (2)
C3—H3A	0.979 (17)	C11—H11A	0.959 (19)
C3—H3B	0.985 (19)	C11—H11B	0.967 (19)
C4—C5	1.510 (2)	C12—H12A	0.921 (15)
C4—H4A	0.961 (16)	C12—H12B	0.983 (18)
C7—O1—C1	111.68 (9)	C5—C6—C1	109.95 (9)
C10—O3—C6	111.26 (9)	O3—C6—C12	104.09 (9)
O1—C1—C2	107.67 (9)	C5—C6—C12	113.16 (11)
O1—C1—C6	107.60 (9)	C1—C6—C12	114.39 (11)
C2—C1—C6	111.62 (10)	O2—C7—O1	120.91 (12)
O1—C1—C9	104.83 (9)	O2—C7—C8	128.72 (14)
C2—C1—C9	112.52 (10)	O1—C7—C8	110.37 (11)
C6—C1—C9	112.15 (9)	C7—C8—C9	105.67 (12)
C3—C2—C1	112.05 (11)	C7—C8—H8A	107.0 (10)
C3—C2—H2A	110.6 (8)	C9—C8—H8A	111.5 (10)
C1—C2—H2A	107.5 (8)	C7—C8—H8B	107.5 (11)
C3—C2—H2B	110.9 (8)	C9—C8—H8B	115.1 (10)
C1—C2—H2B	107.7 (8)	H8A—C8—H8B	109.6 (15)
H2A—C2—H2B	107.9 (11)	C8—C9—C1	105.12 (10)
C2—C3—C4	110.93 (12)	C8—C9—H9A	113.7 (9)
C2—C3—H3A	109.0 (9)	C1—C9—H9A	108.6 (9)
C4—C3—H3A	110.8 (9)	C8—C9—H9B	111.3 (9)
C2—C3—H3B	109.6 (10)	C1—C9—H9B	111.7 (8)
C4—C3—H3B	111.0 (9)	H9A—C9—H9B	106.4 (11)
H3A—C3—H3B	105.4 (13)	O4—C10—O3	121.12 (12)
C5—C4—C3	110.85 (13)	O4—C10—C11	128.72 (12)
C5—C4—H4A	110.5 (9)	O3—C10—C11	110.16 (11)
C3—C4—H4A	111.8 (9)	C10—C11—C12	104.62 (11)
C5—C4—H4B	110.4 (8)	C10—C11—H11A	110.2 (11)
C3—C4—H4B	107.4 (8)	C12—C11—H11A	114.4 (11)
H4A—C4—H4B	105.6 (13)	C10—C11—H11B	105.9 (11)
C4—C5—C6	112.85 (12)	C12—C11—H11B	111.2 (10)
C4—C5—H5A	111.3 (7)	H11A—C11—H11B	110.1 (14)
C6—C5—H5A	107.2 (8)	C11—C12—C6	103.88 (11)
C4—C5—H5B	111.6 (8)	C11—C12—H12A	114.6 (9)
C6—C5—H5B	108.2 (8)	C6—C12—H12A	111.0 (9)
H5A—C5—H5B	105.3 (12)	C11—C12—H12B	108.2 (9)
O3—C6—C5	107.50 (10)	C6—C12—H12B	112.2 (10)
O3—C6—C1	107.18 (8)	H12A—C12—H12B	107.1 (13)
C7—O1—C1—C2	109.29 (11)	C9—C1—C6—C5	73.62 (12)
C7—O1—C1—C6	−130.26 (10)	O1—C1—C6—C12	59.78 (12)
C7—O1—C1—C9	−10.72 (12)	C2—C1—C6—C12	177.70 (10)
O1—C1—C2—C3	172.78 (11)	C9—C1—C6—C12	−54.99 (13)
C6—C1—C2—C3	54.90 (14)	C1—O1—C7—O2	−177.58 (11)
C9—C1—C2—C3	−72.21 (15)	C1—O1—C7—C8	1.85 (15)
C1—C2—C3—C4	−55.13 (17)	O2—C7—C8—C9	−172.54 (13)
C2—C3—C4—C5	55.12 (18)	O1—C7—C8—C9	8.09 (17)
C3—C4—C5—C6	−56.16 (17)	C7—C8—C9—C1	−14.03 (16)
C10—O3—C6—C5	−103.82 (11)	O1—C1—C9—C8	15.00 (13)
C10—O3—C6—C1	138.02 (10)	C2—C1—C9—C8	−101.72 (13)
C10—O3—C6—C12	16.46 (13)	C6—C1—C9—C8	131.45 (12)
C4—C5—C6—O3	−61.29 (14)	C6—O3—C10—O4	177.81 (11)
C4—C5—C6—C1	55.06 (14)	C6—O3—C10—C11	−1.99 (14)
C4—C5—C6—C12	−175.66 (12)	O4—C10—C11—C12	166.63 (14)
O1—C1—C6—O3	−55.05 (11)	O3—C10—C11—C12	−13.59 (18)
C2—C1—C6—O3	62.87 (12)	C10—C11—C12—C6	22.61 (18)
C9—C1—C6—O3	−169.83 (9)	O3—C6—C12—C11	−23.69 (15)
O1—C1—C6—C5	−171.61 (9)	C5—C6—C12—C11	92.71 (15)
C2—C1—C6—C5	−53.69 (13)	C1—C6—C12—C11	−140.31 (13)