(2S)-2-(3-Oxo-1,4-dioxaspiro­[4.5]decan-2-yl)ethanoic acid

Tsai, Y.-F.; Su, Y.-T.; Lin, C.-H.

doi:10.1107/S160053680801146X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o939

doi:10.1107/S160053680801146X

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(2S)-2-(3-Oxo-1,4-dioxaspiro[4.5]decan-2-yl)ethanoic acid

Yow-Fu Tsai,^a ^* Yu-Ting Su ^a and Chia-Her Lin ^a

^aDepartment of Chemistry, Chung-Yuan Christian University, Chung-Li 320, Taiwan
^*Correspondence e-mail: tsaiyofu@cycu.edu.tw

(Received 11 March 2008; accepted 22 April 2008; online 30 April 2008)

The title compound, C₁₀H₁₄O₅, is an intermediate in our study of the asymmetric synthesis of α-hydroxyalkanoic acids. The structure consists of 1,4-dioxaspiro[4,5]decane skeleton formed when the cyclohexylidene group binds to both of the hydroxyl groups of carboxylic groups of the starting malic acid. The six-membered ring adopts a chair conformation.

Related literature

For related literature, see: Coppola & Schuster (1997 ); Díez et al. (2001 ); Dixon et al. (2005 ); Hanessian et al. (1993 ); Heimgartner & Obrecht (1990 ); Horgen et al. (2000 ); Liang et al. (2000 ); Sitachitta et al. (2000 ); Sugiyama et al. (1990 ).

Experimental

Crystal data

C₁₀H₁₄O₅
M_r = 214.21
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.7098 (6) Å
b = 10.3463 (8) Å
c = 15.3175 (13) Å
V = 1063.37 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 295 (2) K
0.50 × 0.45 × 0.35 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scanSADABS; Bruker, 2004 ) T_min = 0.948, T_max = 0.963
7861 measured reflections
2206 independent reflections
1814 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.123
S = 1.05
2206 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680801146X/wk2081sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680801146X/wk2081Isup2.hkl

checkCIF report

Comment top

Enantiomerically pure α-hydroxy carboxylic acids are an important class of biological molecules (Liang et al., 2000; Sitachitta et al., 2000; Horgen et al., 2000) as well as important intermediates for the synthesis of natural products (Coppola & Schuster, 1997; Sugiyama et al., 1990; Heimgartner & Obrecht, 1990). For the above reasons, asymmetric synthesis of α-hydroxy carboxylic acids has attracted considerable attention. A number of synthetic strategies for preparing the optically active α-hydroxy carboxylic acids have been published in the literature (Dixon et al., 2005; Díez et al., 2001; Coppola & Schuster, 1997). The synthesis of the optically pure title compound ([a] ²⁰ _D = + 6.6°) (Scheme 1), which is an intermediate of our study on the asymmetric synthesis of α-hydroxyalkanoic acids, was carried out according to the reported method (Hanessian et al., 1993) starting with the commercial optical pure L-(-)-malic acid. Herein, we report the single-crystal structure (Fig. 1) of the title compound. The crude product was recrystalized from ethyl acetate – n-hexane at room temperature, which allowed us to observe the single-crystal of the title compound. Notably, the cyclohexylidene group was bonded at the hydroxyl groups of carboxylic group (C-1) and on C-2 to show the spirocyclic structure.

Related literature top

For related literature, see: Coppola & Schuster (1997); Díez et al. (2001); Dixon et al. (2005); Hanessian et al. (1993); Heimgartner & Obrecht (1990); Horgen et al. (2000); Liang et al. (2000); Sitachitta et al. (2000); Sugiyama et al. (1990).

Experimental top

Freshly distilled cyclohexanone (5.60 ml, 56.00 mmol) and BF₃˙OEt₂ (9.40 ml, 73.30 mmol) was added to a suspension solution of L-(-)-malic acid (5.01 g, 37.39 mmol) in dry ether (62.0 ml) cooled at 0 ^oC. The suspension gradually turned into a clear solution. After the mixture was stirred for 1 h at 0 ^oC, the ice bath was then removed and the mixture was stirred for 12 h at room temperature. The reaction mixture was diluted with ether and washed with 10% aqueous NaOAc (4 x 20.0 ml). The combined aqueous layers were extracted with ether, and the combined organic phases were washed three times with brine and dried over MgSO₄. Removal of solvent in vacuo afforded a crude acid as pale yellow oil. Recrystallization (ethyl acetate /n-hexane) afforded 4.426 g (83%) of the acid 2 as an off-white crystal: Rf = 0.40 (ethyl acetate – n-hexane, 1/1, v/v); [a] ²¹_D = + 6.6° (c 1.2, CHCl3); ¹H NMR (300 MHz, CDCl3) δ 9.29 (bs, 1H), 4.72 (dd, 1H, J = 6.3, 3.9 Hz), 2.99 and 2.86 (ABX, 2H, J_AB = 17.3, J_AX = 6.3, J_BX = 3.9 Hz), 1.89–1.30 (m, 10H).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing the atom numbering scheme. Displacement ellipsoids for non-H atoms are represented at the 30% probability level. The H atoms are drawn with an arbitrary radius.

(2S)-2-(3-Oxo-1,4-dioxaspiro[4.5]decan-2-yl)ethanoic acid top

Crystal data top

C₁₀H₁₄O₅	F(000) = 456
M_r = 214.21	D_x = 1.338 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3702 reflections
a = 6.7098 (6) Å	θ = 2.4–31.6°
b = 10.3463 (8) Å	µ = 0.11 mm⁻¹
c = 15.3175 (13) Å	T = 295 K
V = 1063.37 (15) Å³	Tabular, colourless
Z = 4	0.50 × 0.45 × 0.35 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2206 independent reflections
Radiation source: fine-focus sealed tube	1814 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 33.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004	h = −10→8
T_min = 0.948, T_max = 0.963	k = −15→9
7861 measured reflections	l = −13→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.0907P)² + 0.0732P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2206 reflections	Δρ_max = 0.31 e Å⁻³
138 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.077 (9)

Crystal data top

C₁₀H₁₄O₅	V = 1063.37 (15) Å³
M_r = 214.21	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.7098 (6) Å	µ = 0.11 mm⁻¹
b = 10.3463 (8) Å	T = 295 K
c = 15.3175 (13) Å	0.50 × 0.45 × 0.35 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2206 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004	1814 reflections with I > 2σ(I)
T_min = 0.948, T_max = 0.963	R_int = 0.022
7861 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.05	Δρ_max = 0.31 e Å⁻³
2206 reflections	Δρ_min = −0.17 e Å⁻³
138 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
O1	0.7046 (2)	0.66387 (12)	0.06930 (8)	0.0516 (3)
O2	0.4717 (2)	0.51238 (14)	0.10628 (8)	0.0584 (4)
O3	0.2465 (2)	0.28916 (12)	0.00641 (11)	0.0613 (4)
O4	−0.0034 (2)	0.40271 (14)	−0.04693 (12)	0.0647 (4)
H4A	−0.0620	0.3336	−0.0414	0.097*
O5	0.6684 (3)	0.66532 (14)	−0.07558 (9)	0.0614 (4)
C1	0.6310 (2)	0.61950 (15)	−0.00602 (11)	0.0438 (3)
C2	0.4985 (3)	0.50524 (14)	0.01414 (10)	0.0406 (3)
H2A	0.5662	0.4245	−0.0015	0.049*
C3	0.2983 (3)	0.51228 (15)	−0.03022 (12)	0.0454 (3)
H3A	0.2220	0.5827	−0.0051	0.055*
H3B	0.3176	0.5309	−0.0917	0.055*
C4	0.1827 (2)	0.38946 (15)	−0.02119 (10)	0.0393 (3)
C5	0.6327 (3)	0.58484 (16)	0.14185 (11)	0.0461 (4)
C6	0.5544 (4)	0.6724 (2)	0.21270 (13)	0.0615 (5)
H6A	0.4875	0.6209	0.2568	0.074*
H6B	0.4577	0.7317	0.1880	0.074*
C7	0.7215 (5)	0.7482 (2)	0.25453 (14)	0.0702 (7)
H7A	0.7760	0.8083	0.2122	0.084*
H7B	0.6687	0.7981	0.3029	0.084*
C8	0.8859 (4)	0.6613 (2)	0.28737 (14)	0.0686 (6)
H8A	0.8347	0.6064	0.3336	0.082*
H8B	0.9925	0.7136	0.3114	0.082*
C9	0.9671 (3)	0.5778 (2)	0.21429 (14)	0.0643 (5)
H9A	1.0289	0.6322	0.1704	0.077*
H9B	1.0681	0.5200	0.2372	0.077*
C10	0.8011 (3)	0.49950 (18)	0.17303 (13)	0.0547 (4)
H10A	0.8540	0.4511	0.1240	0.066*
H10B	0.7502	0.4381	0.2154	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0599 (8)	0.0417 (6)	0.0531 (6)	−0.0192 (6)	−0.0063 (6)	0.0093 (5)
O2	0.0631 (8)	0.0668 (8)	0.0454 (6)	−0.0280 (7)	−0.0004 (6)	0.0098 (6)
O3	0.0445 (6)	0.0356 (5)	0.1039 (11)	−0.0022 (5)	−0.0091 (7)	0.0121 (7)
O4	0.0425 (6)	0.0513 (7)	0.1003 (11)	−0.0049 (6)	−0.0158 (7)	0.0192 (7)
O5	0.0622 (8)	0.0654 (9)	0.0565 (7)	−0.0148 (7)	0.0016 (6)	0.0219 (7)
C1	0.0436 (7)	0.0370 (6)	0.0509 (8)	−0.0079 (6)	0.0021 (7)	0.0086 (6)
C2	0.0434 (7)	0.0330 (6)	0.0455 (7)	−0.0058 (6)	−0.0007 (6)	0.0048 (6)
C3	0.0436 (7)	0.0360 (7)	0.0568 (8)	−0.0043 (6)	−0.0036 (7)	0.0096 (6)
C4	0.0376 (6)	0.0365 (6)	0.0440 (7)	−0.0006 (6)	−0.0002 (6)	0.0009 (5)
C5	0.0516 (9)	0.0420 (7)	0.0448 (7)	−0.0098 (7)	−0.0003 (7)	0.0040 (6)
C6	0.0602 (11)	0.0677 (12)	0.0564 (10)	0.0122 (10)	−0.0036 (9)	−0.0061 (9)
C7	0.0984 (19)	0.0535 (11)	0.0588 (11)	0.0035 (11)	−0.0118 (12)	−0.0117 (9)
C8	0.0772 (15)	0.0712 (13)	0.0575 (10)	−0.0108 (12)	−0.0193 (10)	−0.0002 (10)
C9	0.0513 (10)	0.0734 (13)	0.0683 (11)	0.0032 (10)	−0.0065 (9)	0.0130 (11)
C10	0.0663 (11)	0.0425 (8)	0.0552 (8)	0.0047 (9)	0.0025 (9)	0.0053 (7)

Geometric parameters (Å, º) top

O1—C1	1.336 (2)	C5—C10	1.511 (3)
O1—C5	1.4617 (19)	C6—C7	1.511 (3)
O2—C5	1.423 (2)	C6—H6A	0.9700
O2—C2	1.425 (2)	C6—H6B	0.9700
O3—C4	1.199 (2)	C7—C8	1.510 (4)
O4—C4	1.317 (2)	C7—H7A	0.9700
O4—H4A	0.8200	C7—H7B	0.9700
O5—C1	1.193 (2)	C8—C9	1.515 (3)
C1—C2	1.511 (2)	C8—H8A	0.9700
C2—C3	1.507 (2)	C8—H8B	0.9700
C2—H2A	0.9800	C9—C10	1.515 (3)
C3—C4	1.495 (2)	C9—H9A	0.9700
C3—H3A	0.9700	C9—H9B	0.9700
C3—H3B	0.9700	C10—H10A	0.9700
C5—C6	1.508 (3)	C10—H10B	0.9700

C1—O1—C5	110.00 (12)	C7—C6—H6A	109.4
C5—O2—C2	108.11 (13)	C5—C6—H6B	109.4
C4—O4—H4A	109.5	C7—C6—H6B	109.4
O5—C1—O1	123.82 (15)	H6A—C6—H6B	108.0
O5—C1—C2	128.12 (16)	C8—C7—C6	111.94 (17)
O1—C1—C2	108.05 (13)	C8—C7—H7A	109.2
O2—C2—C3	109.37 (15)	C6—C7—H7A	109.2
O2—C2—C1	103.66 (13)	C8—C7—H7B	109.2
C3—C2—C1	113.23 (12)	C6—C7—H7B	109.2
O2—C2—H2A	110.1	H7A—C7—H7B	107.9
C3—C2—H2A	110.1	C7—C8—C9	110.88 (17)
C1—C2—H2A	110.1	C7—C8—H8A	109.5
C4—C3—C2	112.30 (13)	C9—C8—H8A	109.5
C4—C3—H3A	109.1	C7—C8—H8B	109.5
C2—C3—H3A	109.1	C9—C8—H8B	109.5
C4—C3—H3B	109.1	H8A—C8—H8B	108.1
C2—C3—H3B	109.1	C10—C9—C8	110.37 (19)
H3A—C3—H3B	107.9	C10—C9—H9A	109.6
O3—C4—O4	122.26 (15)	C8—C9—H9A	109.6
O3—C4—C3	125.67 (15)	C10—C9—H9B	109.6
O4—C4—C3	112.07 (14)	C8—C9—H9B	109.6
O2—C5—O1	104.72 (12)	H9A—C9—H9B	108.1
O2—C5—C6	109.10 (17)	C5—C10—C9	111.66 (15)
O1—C5—C6	109.04 (14)	C5—C10—H10A	109.3
O2—C5—C10	112.38 (15)	C9—C10—H10A	109.3
O1—C5—C10	108.68 (15)	C5—C10—H10B	109.3
C6—C5—C10	112.58 (15)	C9—C10—H10B	109.3
C5—C6—C7	111.0 (2)	H10A—C10—H10B	107.9
C5—C6—H6A	109.4

Experimental details

Crystal data
Chemical formula	C₁₀H₁₄O₅
M_r	214.21
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	6.7098 (6), 10.3463 (8), 15.3175 (13)
V (Å³)	1063.37 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.50 × 0.45 × 0.35

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004
T_min, T_max	0.948, 0.963
No. of measured, independent and observed [I > 2σ(I)] reflections	7861, 2206, 1814
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.772

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.123, 1.05
No. of reflections	2206
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.17

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We gratefully acknowledge financial support in part from the National Science Council, Taiwan (NSC 96-2113-M-033-003) and in part from the project of the specific research fields in the Chung Yuan Christian University, Taiwan, under grant CYCU-95-CR-CH.

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