(3R*,4R*,5S*)-4-(4-Methyl­phen­yl)-2,3-diphenyl-7-[(R*)-1-phenyl­ethyl]-1-oxa-2,7-diaza­spiro­[4.5]decan-10-one oxime

G Chanthini Begum; R Suresh Kumar; J Suresh; C Gopinathan; P L Nilantha Lakshman

doi:10.1107/S1600536808004121

. 2008 Feb 15;64(Pt 3):o590. doi: 10.1107/S1600536808004121

(3R,4R,5S)-4-(4-Methylphenyl)-2,3-diphenyl-7-[(R)-1-phenylethyl]-1-oxa-2,7-diazaspiro[4.5]decan-10-one oxime

G Chanthini Begum ^a, R Suresh Kumar ^b, J Suresh ^a, C Gopinathan ^a, P L Nilantha Lakshman ^c,^*

PMCID: PMC2960745 PMID: 21201928

Abstract

In the title compound, C₃₄H₃₅N₃O₂, the polysubstituted piperidine ring adopts a chair conformation and the isoxazolidine ring is in an envelope form. The molecules are linked into a chain along the b axis by O—H⋯N, C—H⋯O and C—H⋯N interactions. The chains are cross-linked via weak C—H⋯π interactions.

Related literature

For related literature, see: Ali et al. (1988 ▶); Annuziata et al. (1987 ▶); Colombi et al. (1978 ▶); Gothelf & Jorgensen (2000 ▶); Goti et al. (1997 ▶); Hossain et al. (1993 ▶); Kumar et al. (2003 ▶).

Experimental

Crystal data

C₃₄H₃₅N₃O₂
M _r = 517.65
Orthorhombic,
a = 10.448 (7) Å
b = 10.588 (9) Å
c = 26.490 (16) Å
V = 2930 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 293 (2) K
0.18 × 0.16 × 0.11 mm

Data collection

Nonius MACH-3 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.986, T _max = 0.991
3068 measured reflections
2933 independent reflections
1037 reflections with I > 2σ(I)
R _int = 0.049
2 standard reflections frequency: 60 min intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.119
S = 0.95
2933 reflections
355 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808004121/ci2561sup1.cif

e-64-0o590-sup1.cif^{(26.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808004121/ci2561Isup2.hkl

e-64-0o590-Isup2.hkl^{(141KB, hkl)}

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

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

Cg1 is the centroid of the C31–C36 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.82	1.98	2.791 (6)	170
C3—H3B⋯N2ⁱⁱ	0.97	2.61	3.353 (8)	133
C96—H96⋯O1ⁱⁱ	0.93	2.60	3.456 (9)	154
C94—H94⋯Cg1ⁱⁱⁱ	0.93	2.80	3.721 (11)	170

Open in a new tab

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

Acknowledgments

RSK thanks CSIR, New Delhi, for a Major Research Project.

supplementary crystallographic information

Comment

1,3-dipolar cycloaddition of nitrones with olefinic dipolarophiles proceeds through a concerted mechanism yielding highly substituted isoxazolidines with generation of as many as three new contiguous stereogenic centers in a single step (Gothelf & Jorgensen, 2000). Isoxazolidines are potential precursors for biologically important compounds such as amino sugars, alkaloids (Goti et al., 1997; Ali et al., 1988), β-lactams (Ali et al., 1988), and amino acids (Annuziata et al., 1987), and exhibit antibacterial and antifungal activities (Kumar et al., 2003). Among the dipoles, nitrones have been extensively used as they readily undergo both inter- and intra-molecular 1,3-dipolar cycloaddition with olefins. 1,3-dipolar cycloaddition of exocyclic olefins with nitrones result in highly substituted spiro-isoxazolidines (Hossain et al., 1993) and they have also been transformed into complex heterocycles (Colombi et al., 1978).

The molecular structure of the title compound is shown in Fig.1. The isoxazolidine ring has an envelope conformation, as indicated by the puckering parameters Q = 0.492 (6) Å and φ = 34.1 (7)°. The piperidine ring adopts a chair conformation. The C31—C36, C81—C86 and C71—C76 phenyl rings form dihedral angles of 37.5 (3)°, 77.5 (3)° and 71.8 (2)°, respectively, with the O2/C5/C7/C8 plane. The C31—C36 and C71—C76 phenyl rings are oriented at angles of 74.1 (3)° and 70.9 (3)°, respectively, with respect to the C81—C86 phenyl ring. The C2—N1—C9—C91 and C6—N1—C9—C10 torsion angles are 175.9 (6) and 178.4 (5)°, respectively.

Intermolecular O—H···N and weak C—H···O and C—H···N interactions form a linear chain running parallel to the b axis (Table 1). The chains are cross-linked via weak C—H···π interactions involving the C31—C36 phenyl ring (centroid Cg1).

Experimental

4-(4-Methylphenyl)-2,3-diphenyl-7-[(R)-1-phenylethyl]-1-oxa-2,7-diazaspiro[4.5] decan-10-one (0.05 g, 0.01 mmol), hydroxylammonium chloride (0.010 g, 0.015 mmol) and sodium acetate (0.012 g, 0.015 mmol) in ethanol (3 ml) was refluxed for 30 min. After completion of the reaction, as evident from TLC the excess solvent was evaporated in vacuo and the residue was subjected to flash column chromatography on silica gel using petroleum ether-ethyl acetate (10:2) as eluent. The product was recrystallized from ethanol (yield 72%, m.p 418 K)