N-{4-Bromo-2-[(S)-menth­yloxy]-5-oxo-2,5-dihydro-3-fur­yl}-l-valine

Xiu-Mei Song; Zhao-Yang Li; Zhao-Yang Wang; Jian-Hua Fu

doi:10.1107/S1600536809026129

. 2009 Jul 11;65(Pt 8):o1838. doi: 10.1107/S1600536809026129

N-{4-Bromo-2-[(S)-menthyloxy]-5-oxo-2,5-dihydro-3-furyl}-l-valine

Xiu-Mei Song ^a, Zhao-Yang Li ^a, Zhao-Yang Wang ^a,^*, Jian-Hua Fu ^a

PMCID: PMC2977280 PMID: 21583539

Abstract

The title compound, C₁₉H₃₀BrNO₅, was obtained via a tandem asymmetric Michael addition–elimination reaction of 3,4-dibromo-5-[(S)-l-menthyloxy]furan-2(5H)-one and l-valine in the presence of potassium hydroxide. The molecular structure contains an approximately planar (r.m.s. deviation = 0.0204 Å) five-membered furanone ring and a six-membered menthyloxy ring adopting a chair conformation. The crystal packing is stabilized by intermolecular O—H⋯O and N—H⋯O hydrogen bonding.

Related literature

For applications of chiral 5-(l-menthyloxy)-2(5H)-furanones, see: Feringa & De Jong (1988 ▶); De Koning et al. (1997 ▶); Lattmann et al. (1999 ▶); He et al. (2006 ▶); Wang et al. (2006 ▶). For biologically active 4-amino-2(5H)-furanones, see: Kimura et al. (2000 ▶); Tanoury et al. (2008 ▶). For related compounds, see: Wang et al. (2006 ▶); Li et al. (2009 ▶). For the synthesis, see: Chen & Geng (1993 ▶).

Experimental

Crystal data

C₁₉H₃₀BrNO₅
M _r = 432.34
Tetragonal,
a = 10.5409 (9) Å
c = 39.388 (7) Å
V = 4376.4 (9) Å³
Z = 8
Mo Kα radiation
μ = 1.91 mm⁻¹
T = 293 K
0.30 × 0.22 × 0.18 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.558, T _max = 0.710
22304 measured reflections
3859 independent reflections
2726 reflections with I > 2σ(I)
R _int = 0.065

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.085
S = 1.03
3859 reflections
241 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.40 e Å⁻³
Absolute structure: Flack (1983 ▶), 1526 Friedel pairs
Flack parameter: −0.001 (11)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); 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/S1600536809026129/xu2542sup1.cif

e-65-o1838-sup1.cif^{(22.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026129/xu2542Isup2.hkl

e-65-o1838-Isup2.hkl^{(185.4KB, 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
N1—H1⋯O5ⁱ	0.86	2.28	3.047 (4)	149
O4—H4⋯O2ⁱⁱ	0.82	1.83	2.615 (3)	160

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The work was supported by the National Natural Science Foundation of China (grant No. 20772035) and the Natural Science Foundation of Guangdong Province, China (grant No. 5300082).

supplementary crystallographic information

Comment

Chiral 5-(l-menthyloxy)-2(5H)-furanones have been utilized as key building blocks in the synthesis of supramolecules and important natural products since 1980's (Feringa & De Jong, 1988; De Koning et al., 1997; Lattmann et al., 1999), especially in asymmetric synthesis (He et al., 2006; Wang et al., 2006). At the same time, 4-amino-2(5H)-furanone is an attractive moiety in chemical, pharmaceutical and agrochemical research. Many 4-amino-2(5H)-furanones have been patented as prodrugs or insecticides and herbicides (Kimura et al., 2000; Tanoury et al., 2008). Attracted by versatile 4-amino-2(5H)-furanones, we synthesized the title compound with chiral synthon 3,4-dibromo-5-(S)-(l-menthyloxy)-2(5H)-furanone and L-valine in the present of potassium hydroxide via the tandem asymmetric Michael addition-elimination reaction. With 2(5H)-furanone moiety and polyfunctional groups (carboxyl, amino, halo), the title compound is expected to be a biologically active product and excellent ligand.

The structure of the title compound is illustrated in Fig. 1. The title compound which has five chiral centers (C2(S), C8(S), C9(R), C10(S), C14(R)) contains a five-membered furanone ring and a six-membered menthyloxy ring connected each other via C8—O3—C9 ether bond. The furanone ring is approximately planar, whereas the cyclohexane ring displays a chair conformation with three substituents occupying equatorial positions. The bond lengths and angles in the title compound are good agreement with the expected values (Wang et al., 2006; Li et al., 2009). In the crystal structure the molecules are linked by intermolecular hydrogen bonds (Table 1).

Experimental

The precursor 3,4-dibromo-5-(S)-(l-menthyloxy)-2(5H)-furanone was prepared according to the literature procedure (Chen et al., 1993). An absolute ethanol solution (5 ml) of L-valine (4.5 mmol) and potassium hydroxide (5.8 mmol) was mixed with the dichloromethane solution (6 ml) of 3,4-dibromo-5-(S)-(l-menthyloxy)-2(5H)-furanone (3.0 mmol) under nitrogen atmosphere. The solution was stirred for 24 h at room temperature, and then the solvents were removed under reduced pressure. The solid residual was dissolved in dichloromethane, and pH of the solution was adjusted to 3 with 15% of aqueous HCl solution. Then the combined organic layers from extraction were concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography with the gradient mixture of petroleum ether and ethyl acetate to give the product yielding (I) 0.9186 g (71.1%). Colorless crystals were obtained in acetone solution by slow evaporation.