Dimethyl [1-(1-allyl-5-iodo-1H-indol-3-yl)-3-hydroxy­prop­yl]phospho­nate

Ying-Cen Guo; Xu-Fan Wang; Yu Ding

doi:10.1107/S1600536807068171

. 2008 Jan 9;64(Pt 2):o384. doi: 10.1107/S1600536807068171

Dimethyl [1-(1-allyl-5-iodo-1H-indol-3-yl)-3-hydroxypropyl]phosphonate

Ying-Cen Guo ^a, Xu-Fan Wang ^a, Yu Ding ^a,^*

PMCID: PMC2960229 PMID: 21201414

Abstract

In the title compound, C₁₆H₂₁INO₄P, the molecular structure is stabilized by a weak intramolecular C—H⋯O hydrogen-bond interaction. The crystal packing is stabilized by strong intermolecular O—H ⋯ O hydogen-bonding interactions to form a zigzag packing arrangement.

Related literature

For asymmetric synthesis of phosphorus compounds, see: Carlone et al. (2007 ▶); Yang, et al. (2007 ▶); Ibrahem et al. (2007 ▶). For related structures, see: Sonar et al. (2006 ▶); Chen et al. (2007 ▶); Butcher et al. (2007 ▶). For related literature, see: Allen et al. (1989 ▶); Horiguchi & Kandatsu (1959 ▶).

Experimental

Crystal data

C₁₆H₂₁INO₄P
M _r = 449.21
Orthorhombic,
a = 7.9983 (4) Å
b = 10.1295 (6) Å
c = 22.3722 (12) Å
V = 1812.57 (17) Å³
Z = 4
Mo Kα radiation
μ = 1.87 mm⁻¹
T = 294 (2) K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T _min = 0.706, T _max = 0.835
10836 measured reflections
3564 independent reflections
3314 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.102
S = 1.04
3564 reflections
211 parameters
H-atom parameters constrained
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.30 e Å⁻³
Absolute structure: Flack (1983 ▶), 1503 Freidel pairs
Flack parameter: 0.00 (1)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Bruker, 2001 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807068171/at2520sup1.cif

e-64-0o384-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068171/at2520Isup2.hkl

e-64-0o384-Isup2.hkl^{(174.8KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O1	0.98	2.47	2.873 (7)	104
O1—H1⋯O4ⁱ	0.82	1.92	2.733 (6)	174

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge financial support from the Natural Science Foundation of Hubei Province of China (No. 2006ABA175) and the Natural Science Foundation of Central China Normal University, and are indebted to Dr Guangmin Yao of Shijiazhuang Pharmaceutical Group, Zhongqi (sjz) Pharmaceutical Technology Co. Ltd, and Professor Wenjing Xiao and Dr Xianggao Meng of Central China Normal University, for their advice and support.

supplementary crystallographic information

Comment

Phosphorus has been recognized as an essential structural constituent of many biomolecules and a crucial element in many biological transformations (Horiguchi & Kandatsu,1959; Allen et al. 1989). With the advances in the development of chiral catalysts, asymmetric synthesis of some phosphorus compounds has been well documented in literatures (Carlone et al., 2007; Yang, et al., 2007; Ibrahem et al., 2007). As part of our ongoing project on enantioselective organocatalysis, a series of α-indolyl phosphonates have been highly enantioselectively synthesized via Friedel-Crafts alkylation of substituted indoles with (E)-dialkyl 3-oxoprop-1-enylphosphonate using MacMillan's imidazolidinone catalysts. The title compound (I) was synthesized and its crystal structure is presented here.

As seen in Fig. 1, the pyrrole plane (C1/C6—C8/N1) and the phenyl ring (C1—C6) are coplanar with each other with a dihedral angle between their mean planes of 2.2 (24)° in the molecule of the title compound (I), and the molecular structure is stablized by a week C12—H12 ··· O1 intramolecular hydrogen bonding interaction (Table 1).

The crystal packing (Fig. 2) is stabilized by strong intermolecular O—H ··· O hydogen bonds interaction (Table 1) to form a zigzag packing arrangement. Dipole–dipole and van der Waals interactions are also effective in the molecular packing in the crystal structure.

Experimental

The MacMillan's imidazolidinone catalysts (Fig 3) (0.02 mmol) and TFA (0.02 mmol) were stirred in 1 ml dichloromethane for 5 min at 195 K, then (E)-dialkyl 3-oxoprop-1-enylphosphonate 2 (0.1 mmol) was added and stirred for 15 min. And then 1-allyl-5-iodo-1H-indole 1 (0.11 mmol) was added. After the mixture was stirred for 48 h, the solvent (dichloromethane) was removed under reduced pressure at room temperature, and then the residue was added to a stirring solution of sodium borohydride (18.6 mg, 0.5 mmol, 5 equiv) in methanol (3.0 ml). After 15 min, the reaction was quenched with saturated aqueous NaHCO₃ and extracted with CH₂Cl₂. The combined organic layer was washed with saturated solutions of NaHCO₃ and NaCl and then dried over with Na₂SO₄. The combined organic layer was concentrated in vacuo and the product was purified by flash column chromatography on silica gel (ethyl acetate, R_f = 0.4), (14.3 mg, 48% yield). Compound 5 m: yellow solid; tr (minor) = 53.8 min, tr (major) = 59.5 min (Chiralcel AD—H, λ = 254 nm, 5% i-PrOH / hexanes, flow rate = 1.0 ml/min). ¹H NMR (400 MHz, CDCl₃) δ 2.10–2.18 (m, 1H), 2.28–2.35 (m, 1H), 2.59 (br, 1H), 3.49 (d, J = 10.8 Hz, 3H), 3.73 (d, J = 10.8 Hz, 3H), 3.50–3.75 (m, 3H), 4.67 (d, J = 5.2 Hz, 2H), 5.00 (d, J = 16.8 Hz, 1H), 5.19 (d, J = 10.4 Hz, 1H), 5.90–6.02 (m, 1H), 7.05–7.47 (m, 3H), 7.98 (s, 1H). ¹³C NMR (100 MHz, CDCl₃) δ 29.9, 31.3, 33.3, 48.9, 52.67, 52.75, 53.4, 53.5, 59.7, 59.8, 83.0, 107.9, 111.8, 117.5, 127.9, 128.5, 129.5, 130.2, 132.8, 135.2.; MS (EI) m/z 449 (M⁺), 450 (M⁺+1), 451 (M⁺+2). Elemental Analysis calculated for C₁₆H₂₁INO₄P: C 42.78, H 4.71, N 3.12%. Found: C 42.58, H 4.94, N 3.99%. [α]23D = -22.62 (C=2.35, CHCl₃) (after recrystallization). Single crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of a CHCl₃ solution.