(S)-N-[(1S,2S)-2-Benzyl­amino-1-(4-hy­droxy­phen­yl)-3-methyl­butyl]-1,1-di­methyl­ethane-2-sulfinamide

Chun Shen

doi:10.1107/S1600536808031073

. 2008 Oct 9;64(Pt 11):o2082. doi: 10.1107/S1600536808031073

(S)-N-[(1S,2S)-2-Benzylamino-1-(4-hydroxyphenyl)-3-methylbutyl]-1,1-dimethylethane-2-sulfinamide

Chun Shen ^a,^*

PMCID: PMC2959556 PMID: 21580947

Abstract

The title compound, C₂₂H₃₂N₂O₂S, was obtained by dehydroxylation and deacetylation of 4-{(1S,2S)-2-(benzylhydroxyamino)-3-methyl-1-[(S)-2-methylpropane-2-sulfinylamino]butyl}phenyl acetate, which was derived from reductive crosslinking of nitrone with N-tert-butanesulfinylimine. The crystal structure shows that the molecules are linked by O—H⋯O hydrogen bonds.

Related literature

For general background on optically pure vicinal diamines, see: Bennai & Hanessian (1997 ▶); Kizirian (2008 ▶). For the synthesis of the starting material, see: Zhong et al. (2004 ▶).

Experimental

Crystal data

C₂₂H₃₂N₂O₂S
M _r = 388.56
Orthorhombic,
a = 9.7503 (9) Å
b = 12.1068 (11) Å
c = 19.6292 (18) Å
V = 2317.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 293 (2) K
0.45 × 0.40 × 0.29 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.783, T _max = 1.000 (expected range = 0.749–0.956)
13756 measured reflections
5016 independent reflections
2765 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.130
S = 0.89
5016 reflections
261 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ▶), with 2249 Friedel pairs
Flack parameter: 0.01 (10)

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 (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808031073/bv2109sup1.cif

e-64-o2082-sup1.cif^{(21.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808031073/bv2109Isup2.hkl

e-64-o2082-Isup2.hkl^{(245.7KB, 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
O1—H1B⋯O2ⁱ	0.828 (19)	1.82 (2)	2.647 (4)	173 (5)

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

Optically pure vicinal diamines are important molecules due to their special structures. Among them, a lot of compounds have been used as catalysts in asymmetric reactions (Bennai & Hanessian, 1997; Kizirian, 2008). In our study of vicinal diamines, we prepared (S)-N-((1S,2S)-2-(benzylamino)-1-(4-hydroxyphenyl) -3-methylbutyl)-2-methylpropane-2-sulfinamide through dehydroxylation and deacetylation of acetic acid 4-[(1S,2S)-2(benzyl-hydroxy-amino)-3-methyl-1- ((S)-2-methyl-propane-2-sulfinylamino)-butyl]-phenyl ester which was prepared according to the reported procedure (Zhong et al., 2004). Here, we report its crystal structure. The molecules are linked by a strong intermolecular O1—H1B···O2ⁱ hydrogen interaction. The molecular packing for the compound is shown in Fig. 3, where hydrogen bond interactions are shown as dashed lines. The two benzene rings are almost perpendicular to each other, making a diheral angle of 84.12(0.12)°. The molecule exists in a trans configuration with an N1—C1—C2—N2 torsion angle of 55.6 (3)°. The absolute configuration was known from the starting chiral material and is confirmed by this X-ray analysis.

Experimental

A mixture of Cu(II) acetate (18 mg, 0.1 mmol), zinc powder (324 mg, 5.0 mmol) and acetic acid (2 ml) was stirred for 15 minutes under a nitrogen atmosphere at room temperature. Then a mixture of acetic acid (2 ml), distilled water (0.7 ml) and acetic acid 4-[(1S,2S)-2(benzyl-hydroxy-amino)-3-methyl -1-((S)-2-methyl-propane-2-sulfinylamino)-butyl]-phenyl ester (Zhong et al., 2004) (446 mg, 1.0 mmol) was added. The resulting mixture was heated to 343 K and stirred for an hour. After cooling to room temperature, ethylene diamine tetraacetic acid disodium salt (0.5 g) was added and stirred for 10 minutes. Aqueous KOH (3N) solution was then added to adjust the mixture to a pH value of 10. The resulting solution was extracted with ethyl acetate, and the combined organic layers were washed with saturated aqueous ethylene diamine tetraacetic acid disodium salt and brine successively. Concentrated under reduced pressure, the crude product was dissolved in MeOH (10 ml) and saturated aqueous NaHCO₃ (10 ml) was added. The mixture was stirred for 12 h at room temperature and then MeOH was removed under reduced pressure. The crude solid was redissolved in CH₂Cl₂, washed with brine and dried with anhydrous Na₂SO₄. After silica gel chromatography, the pure product was obtained as a white solid (yield 77% over two steps). Suitable crystals for the X-ray diffraction experiment were obtained by recrystalization from hexane/CH₂Cl₂ (3:1). Spectroscopic data: ¹H NMR (300 MHz, CDCl₃) δ 7.36–7.24 (m, 5H), 7.11 (d, J = 6.0 Hz, 2H), 6.80 (d, J = 5.7 Hz, 2H), 5.49 (s, 1H), 4.02 (m, 2H), 3.77 (d, J = 13.2 Hz, 1H), 2.63(d, J = 9.3 Hz, 1H), 1.72 (m, 2H), 1.14 (s, 9H), 0.95 (d, J = 4.5 Hz, 3H), 0.77 (d, J = 4.5 Hz, 3H). ESI-MS (m/z): 389(M+H⁺).