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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1109.
Published online 2010 April 17. doi:  10.1107/S1600536810013139
PMCID: PMC2979223

(3aR*,7aS*)-1-(p-Tolyl­sulfon­yl)perhydro­indol-2-one

Abstract

In the racemic title compound, C15H19NO3S, the dihedral angle between the planes of the benzene ring and the O=S=O group is 56.92 (7)° and the cyclo­hexane ring adopts a chair conformation.

Related literature

For related structures, see: Brion et al. (1992 [triangle]). For the medicinal background, see: De Ponti et al. (1991 [triangle]).

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Object name is e-66-o1109-scheme1.jpg

Experimental

Crystal data

  • C15H19NO3S
  • M r = 293.37
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1109-efi1.jpg
  • a = 15.6509 (12) Å
  • b = 5.9692 (5) Å
  • c = 15.7967 (13) Å
  • V = 1475.8 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.23 mm−1
  • T = 120 K
  • 0.25 × 0.20 × 0.18 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.946, T max = 0.961
  • 7103 measured reflections
  • 2702 independent reflections
  • 2397 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.102
  • S = 1.01
  • 2702 reflections
  • 182 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.17 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1189 Friedel pairs
  • Flack parameter: 0.01 (10)

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810013139/hb5400sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013139/hb5400Isup2.hkl

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

Acknowledgments

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

supplementary crystallographic information

Comment

Trandolapril, a potent angiotensin-converting enzyme (ACE) inhibitor, has been widely used for the treatment of hypertension (De Ponti et al., 1991). However, its synthesis procedure is relatively complicated, especially to construct the stereochemical centers of the molecule. To solve the problem, many methods have been proposed in the past years (Brion et al., 1992). Introducing chiral auxiliary-induced stereoselective groups is one of the most promising synthetic strategies since it requires fewer reactions steps and lead to high enantioselectivity. Currently, using p-toluenesulfonyl group as stereoselectivity-inducing group, we have successfully synthesized the title compound as a key intermediate for the synthesis of trandolapril.

In the compound, the S=O distances are 1.4261 (19) and 1.426 (2) Å, and the angle of O=S=O is 119.20 (12)deg. The angle of the benzene ring and the plane of O=S=O is 56.92 (7) deg. Meanwhile, the cyclohexane portion adpots a chair structure.

Experimental

Chloramine-T (2.3 g, 10 mmol) was reacted with iodine (0.2 g, 1 mmol) and cyclohexene (2.05 g, 25 mmol) in acetonitrile (15 ml) for 19 h at room temperature to give N-(p-toluenesulfonyl)-[b,c] -cyclohexeneaziridine-1H-indole-2-one in a yield of 86%. The crude product was directly treated with diethylmalonate (2.4 g, 15 mmol) and sodium ethoxide (1 g, 15 mmol) in THF at room temperature, offering (3aR, 7aS)-N -(p-toluenesulfonyl)- 3-ethoxycarbonyloctahydro-1H-indole-2-one in a yield of 70%. The obtained compound, together with water (0.2 ml) and sodium chloride (0.35 g), was then dissolved in DMF and warmed to 145 deg for 18 h to yield the title compound in 65% yield as colourless blocks.

Refinement

All the H atoms were positioned geometrically and refined using a riding model with C—H = 0.95-1.00 Å, and with Uiso(H) = 1.5 for the H atoms of methyl group and 1.2 Uiso(C) for other H atoms.

Figures

Fig. 1.
Structure of (I) with 30% displacement ellipsoids.

Crystal data

C15H19NO3SF(000) = 624
Mr = 293.37Dx = 1.320 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 2285 reflections
a = 15.6509 (12) Åθ = 2.6–25.2°
b = 5.9692 (5) ŵ = 0.23 mm1
c = 15.7967 (13) ÅT = 120 K
V = 1475.8 (2) Å3Block, colorless
Z = 40.25 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer2702 independent reflections
Radiation source: fine-focus sealed tube2397 reflections with I > 2σ(I)
graphiteRint = 0.024
[var phi] and ω scanθmax = 26.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −19→19
Tmin = 0.946, Tmax = 0.961k = −7→7
7103 measured reflectionsl = −19→19

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.102w = 1/[σ2(Fo2) + (0.0603P)2 + 0.1589P] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
2702 reflectionsΔρmax = 0.24 e Å3
182 parametersΔρmin = −0.17 e Å3
1 restraintAbsolute structure: Flack (1983), 1189 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.01 (10)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)

xyzUiso*/Ueq
S1−0.00414 (4)0.18513 (9)0.40616 (5)0.03841 (17)
C1−0.0558 (2)0.0780 (5)0.56190 (17)0.0516 (7)
C2−0.0387 (2)−0.1072 (6)0.62443 (18)0.0629 (9)
H2A−0.0509−0.05770.68300.075*
H2B−0.0737−0.24100.61160.075*
C30.0549 (2)−0.1554 (5)0.61272 (16)0.0489 (7)
H3A0.0873−0.03470.64260.059*
C40.0933 (2)−0.3773 (5)0.63948 (19)0.0663 (9)
H4A0.0644−0.50140.60930.080*
H4B0.0850−0.39950.70100.080*
C50.1881 (2)−0.3783 (6)0.61869 (18)0.0703 (10)
H5A0.2118−0.52870.63070.084*
H5B0.2178−0.26940.65570.084*
C60.2056 (2)−0.3187 (6)0.5266 (2)0.0691 (10)
H6A0.1856−0.44310.49030.083*
H6B0.2681−0.30430.51850.083*
C70.16246 (19)−0.1007 (5)0.49752 (18)0.0569 (8)
H7A0.18720.02920.52770.068*
H7B0.1708−0.07890.43600.068*
C80.06903 (17)−0.1222 (4)0.51752 (16)0.0395 (6)
H8A0.0461−0.25620.48710.047*
C9−0.10350 (16)0.0904 (4)0.36999 (14)0.0342 (5)
C10−0.10958 (16)−0.1217 (4)0.33444 (15)0.0376 (5)
H10A−0.0614−0.21830.33320.045*
C11−0.18653 (18)−0.1900 (4)0.30096 (15)0.0405 (6)
H11A−0.1912−0.33570.27730.049*
C12−0.25761 (16)−0.0497 (4)0.30111 (15)0.0391 (6)
C13−0.25008 (16)0.1610 (4)0.33775 (17)0.0403 (6)
H13A−0.29810.25850.33850.048*
C14−0.17402 (17)0.2307 (4)0.37301 (15)0.0374 (6)
H14A−0.17000.37370.39910.045*
C15−0.3410 (2)−0.1241 (5)0.26208 (19)0.0546 (7)
H15A−0.3581−0.26810.28660.066*
H15B−0.3337−0.14080.20080.066*
H15C−0.3852−0.01190.27350.066*
N10.01047 (13)0.0708 (3)0.50183 (13)0.0401 (5)
O1−0.11421 (15)0.2106 (4)0.55905 (13)0.0689 (6)
O2−0.00807 (12)0.4227 (3)0.41542 (15)0.0541 (6)
O30.06024 (11)0.0901 (3)0.35308 (11)0.0479 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0388 (4)0.0307 (3)0.0457 (3)−0.0040 (2)−0.0067 (3)0.0048 (3)
C10.0526 (19)0.0666 (18)0.0355 (12)0.0096 (15)−0.0052 (12)−0.0115 (13)
C20.064 (2)0.089 (2)0.0359 (13)0.0132 (19)0.0076 (14)0.0059 (14)
C30.060 (2)0.0554 (16)0.0316 (11)0.0074 (14)−0.0060 (12)−0.0037 (11)
C40.096 (3)0.0637 (19)0.0396 (15)0.0170 (18)−0.0036 (16)0.0128 (13)
C50.089 (3)0.079 (2)0.0424 (15)0.038 (2)−0.0088 (16)0.0009 (14)
C60.073 (2)0.088 (2)0.0465 (16)0.0378 (19)−0.0027 (16)0.0060 (15)
C70.046 (2)0.0692 (19)0.0554 (17)0.0109 (14)−0.0035 (14)0.0126 (15)
C80.0482 (16)0.0333 (12)0.0370 (12)0.0049 (11)−0.0065 (11)−0.0023 (10)
C90.0394 (15)0.0287 (11)0.0346 (11)−0.0015 (9)−0.0004 (11)0.0042 (9)
C100.0437 (16)0.0320 (12)0.0370 (11)0.0077 (10)0.0004 (12)0.0007 (10)
C110.0502 (17)0.0343 (13)0.0370 (12)−0.0016 (11)−0.0008 (11)−0.0045 (9)
C120.0418 (16)0.0415 (13)0.0340 (11)−0.0054 (11)−0.0030 (10)0.0033 (10)
C130.0375 (16)0.0408 (13)0.0425 (12)0.0045 (10)−0.0036 (11)0.0005 (10)
C140.0412 (16)0.0298 (11)0.0414 (11)0.0022 (10)−0.0015 (11)−0.0017 (10)
C150.047 (2)0.0621 (18)0.0543 (16)−0.0116 (14)−0.0083 (13)−0.0042 (14)
N10.0433 (14)0.0376 (12)0.0394 (11)0.0038 (9)−0.0038 (9)−0.0045 (9)
O10.0639 (15)0.0967 (17)0.0462 (11)0.0313 (13)−0.0031 (10)−0.0131 (11)
O20.0524 (13)0.0302 (9)0.0797 (15)−0.0061 (8)−0.0220 (11)0.0006 (11)
O30.0392 (11)0.0581 (11)0.0463 (10)−0.0009 (8)0.0028 (8)0.0126 (8)

Geometric parameters (Å, °)

S1—O21.4267 (17)C6—H6B0.9900
S1—O31.4281 (19)C7—C81.502 (4)
S1—N11.674 (2)C7—H7A0.9900
S1—C91.750 (2)C7—H7B0.9900
C1—O11.210 (3)C8—N11.493 (3)
C1—N11.406 (4)C8—H8A1.0000
C1—C21.507 (4)C9—C141.386 (3)
C2—C31.505 (5)C9—C101.388 (3)
C2—H2A0.9900C10—C111.377 (4)
C2—H2B0.9900C10—H10A0.9500
C3—C41.514 (4)C11—C121.392 (4)
C3—C81.533 (3)C11—H11A0.9500
C3—H3A1.0000C12—C131.389 (3)
C4—C51.520 (5)C12—C151.510 (4)
C4—H4A0.9900C13—C141.379 (3)
C4—H4B0.9900C13—H13A0.9500
C5—C61.522 (4)C14—H14A0.9500
C5—H5A0.9900C15—H15A0.9800
C5—H5B0.9900C15—H15B0.9800
C6—C71.537 (4)C15—H15C0.9800
C6—H6A0.9900
O2—S1—O3119.03 (12)C8—C7—C6107.0 (3)
O2—S1—N1108.56 (11)C8—C7—H7A110.3
O3—S1—N1105.77 (10)C6—C7—H7A110.3
O2—S1—C9108.42 (10)C8—C7—H7B110.3
O3—S1—C9107.88 (12)C6—C7—H7B110.3
N1—S1—C9106.52 (11)H7A—C7—H7B108.6
O1—C1—N1123.5 (3)N1—C8—C7119.8 (2)
O1—C1—C2129.7 (3)N1—C8—C3100.0 (2)
N1—C1—C2106.8 (2)C7—C8—C3111.0 (2)
C3—C2—C1103.5 (2)N1—C8—H8A108.5
C3—C2—H2A111.1C7—C8—H8A108.5
C1—C2—H2A111.1C3—C8—H8A108.5
C3—C2—H2B111.1C14—C9—C10120.7 (2)
C1—C2—H2B111.1C14—C9—S1120.07 (17)
H2A—C2—H2B109.0C10—C9—S1119.17 (18)
C2—C3—C4121.3 (3)C11—C10—C9119.0 (2)
C2—C3—C8103.7 (2)C11—C10—H10A120.5
C4—C3—C8109.3 (2)C9—C10—H10A120.5
C2—C3—H3A107.3C10—C11—C12121.3 (2)
C4—C3—H3A107.3C10—C11—H11A119.3
C8—C3—H3A107.3C12—C11—H11A119.3
C3—C4—C5109.3 (3)C13—C12—C11118.5 (2)
C3—C4—H4A109.8C13—C12—C15120.7 (2)
C5—C4—H4A109.8C11—C12—C15120.8 (2)
C3—C4—H4B109.8C14—C13—C12121.0 (2)
C5—C4—H4B109.8C14—C13—H13A119.5
H4A—C4—H4B108.3C12—C13—H13A119.5
C4—C5—C6112.4 (3)C13—C14—C9119.4 (2)
C4—C5—H5A109.1C13—C14—H14A120.3
C6—C5—H5A109.1C9—C14—H14A120.3
C4—C5—H5B109.1C12—C15—H15A109.5
C6—C5—H5B109.1C12—C15—H15B109.5
H5A—C5—H5B107.9H15A—C15—H15B109.5
C5—C6—C7113.8 (2)C12—C15—H15C109.5
C5—C6—H6A108.8H15A—C15—H15C109.5
C7—C6—H6A108.8H15B—C15—H15C109.5
C5—C6—H6B108.8C1—N1—C8111.4 (2)
C7—C6—H6B108.8C1—N1—S1119.73 (18)
H6A—C6—H6B107.7C8—N1—S1123.25 (16)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5400).

References

  • Brion, F., Marie, C., Mackiewicz, P., Roul, J. M. & Buendia, J. (1992). Tetrahedron Lett.33, 4889–4892.
  • Bruker (2000). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • De Ponti, F., Marelli, C., D’Angelo, L., Caravaggi, M., Bianco, L., Lecchini, S., Frigo, G. M. & Crema, A. (1991). Eur. J. Clin. Pharmacol.40, 149–153. [PubMed]
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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