(+)-(1S,5R,6R)-6-[(S)-1-Hy­droxy-2-(meth­oxy­meth­yloxy)eth­yl]-1-methyl-3-trichloro­methyl-2-aza-4,7-dioxa­bicyclo­[3.3.0]oct-2-en-8-one

Takeshi Oishi; Hiroki Oishi; Syun Tsuzaki; Takaaki Sato; Noritaka Chida

doi:10.1107/S1600536812042912

. 2012 Oct 20;68(Pt 11):o3185. doi: 10.1107/S1600536812042912

(+)-(1S,5R,6R)-6-[(S)-1-Hydroxy-2-(methoxymethyloxy)ethyl]-1-methyl-3-trichloromethyl-2-aza-4,7-dioxabicyclo[3.3.0]oct-2-en-8-one

Takeshi Oishi ^a,^*, Hiroki Oishi ^b, Syun Tsuzaki ^b, Takaaki Sato ^b, Noritaka Chida ^b

PMCID: PMC3515276 PMID: 23284496

Abstract

In the title compound, C₁₁H₁₄Cl₃NO₆, the fused five-membered oxazoline and tetrahydrofuran rings are essentially planar with maximum deviations of 0.069 (1) and 0.031 (1) Å, respectively, and make a dihedral angle of 64.23 (11)° with each other. In the crystal, molecules are linked by O—H⋯O and C—H⋯O hydrogen bonds, forming chains along the b-axis direction. Further C—H⋯O hydrogen bonds are observed between the chains.

Related literature

For the synthesis, see: Oishi et al. (2012 ▶). For the isolation of sphingofungins, see: VanMiddlesworth, Giacobbe et al. (1992 ▶); VanMiddlesworth, Dufresne et al. (1992 ▶); Horn et al. (1992 ▶).

Experimental

Crystal data

C₁₁H₁₄Cl₃NO₆
M _r = 362.58
Monoclinic,
a = 8.9311 (7) Å
b = 6.0283 (4) Å
c = 13.8694 (10) Å
β = 99.699 (2)°
V = 736.05 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.65 mm⁻¹
T = 90 K
0.50 × 0.25 × 0.16 mm

Data collection

Bruker D8 goniometer diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ▶) T _min = 0.738, T _max = 0.904
6662 measured reflections
2364 independent reflections
2291 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.069
S = 1.34
2364 reflections
193 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: Flack (1983 ▶), 947 Friedel pairs
Flack parameter: 0.01 (5)

Data collection: APEX2 (Bruker, 2012 ▶); cell refinement: SAINT (Bruker, 2012 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Click here for additional data file.^{(24.1KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812042912/is5207sup1.cif

e-68-o3185-sup1.cif^{(24.1KB, cif)}

Click here for additional data file.^{(116.2KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812042912/is5207Isup2.hkl

e-68-o3185-Isup2.hkl^{(116.2KB, hkl)}

Click here for additional data file.^{(3.4KB, cdx)}

Supplementary material file. DOI: 10.1107/S1600536812042912/is5207Isup3.cdx

Click here for additional data file.^{(6KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812042912/is5207Isup4.cml

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
O12—H12⋯O15ⁱ	0.84	1.90	2.695 (2)	157
C6—H6⋯O9ⁱⁱ	1.00	2.43	3.402 (3)	164
C17—H17C⋯O9ⁱⁱⁱ	0.98	2.53	3.320 (3)	137

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

Acknowledgments

We thank Professor S. Ohba, Professor N. Yoshioka and Dr C. Maeda (Keio University, Japan) for providing valuable advice.

supplementary crystallographic information

Comment

Sphingofungins are natural antifungal agents isolated from Aspergillus and reported to be potent inhibitors of the biosynthesis of sphingolipids (VanMiddlesworth, Giacobbe et al., 1992; VanMiddlesworth, Dufresne et al., 1992; Horn et al., 1992). The title compound (I), C₁₁H₁₄Cl₃NO₆, which has four contiguous stereogenic center including a tetra-substituted carbon with nitrogen (Fig. 1), was provided in a synthetic study on the natural products sphingofungins from _D-ribose (Oishi et al., 2012). The absolute configurations were confirmed by the X-ray analysis as C1S, C5R, C6R and C10S. The crystal packing was stabilized by an intermolecular O—H···O hydrogen bond, forming molecular a chain along the b axis (Fig. 2). There are also C—H···O hydrogen bonds and intermolecular Cl···O short contacts, Cl19···O4 (x, y - 1, z) and Cl20···O7 (x + 1, y, z) being 3.070 (2) and 3.142 (2) Å, respectively.

Experimental

The title compound was obtained in a synthetic study of sphingofungins from _D-ribose (Oishi et al., 2012), and recrystallized from ethyl acetate solution. [α]²⁷_D +83.1 (c 0.345, CHCl₃); m.p. 409.7–411.2 K.