(1R,2R,3R,4R,5S)-2,3-Bis[(2S′)-2-acet­oxy-2-phenyl­acet­oxy]-4-azido-1-[(2,4-dinitro­phen­yl)hydrazono­meth­yl]bicyclo­[3.1.0]hexa­ne

Jing Li; Todd L Lowary; Robert McDonald

doi:10.1107/S1600536808000718

. 2008 Jan 16;64(Pt 2):o459–o460. doi: 10.1107/S1600536808000718

(1R,2R,3R,4R,5S)-2,3-Bis[(2S′)-2-acetoxy-2-phenylacetoxy]-4-azido-1-[(2,4-dinitrophenyl)hydrazonomethyl]bicyclo[3.1.0]hexane

Jing Li ^a, Todd L Lowary ^a, Robert McDonald ^b,^*

PMCID: PMC2960152 PMID: 21201486

Abstract

In the title compound, C₃₈H₂₉N₇O₁₂, the five-membered ring adopts an envelope conformation in which the ‘flap’ is cis to the cyclopropane group. This conformation is similar to those of other bicyclo[3.1.0]hexane analogues for which crystal structures have been reported. The absolute configuration of the stereogenic centers on the cyclopentane ring, as determined by comparison with the known configurations of the stereogenic centers in the (2S)-2-acetoxy-2-phenylacetoxy groups, is 1(R), 2(R), 3(R), 4(R) and 5(S). An intramolecular N—H⋯O hydrogen bond is present.

Related literature

For the synthesis of mimetics of biologically important furanoside rings, see: Callam & Lowary (2000 ▶); Callam & Lowary (2001 ▶); Callam et al. (2001 ▶); Centrone & Lowary (2002 ▶). For examples of the crystal structures of bicyclo[3.1.0]hexane systems, see: Gurskaya et al. (1990 ▶, 1996 ▶); Gallucci et al. (2000 ▶); Garcia et al. (1992 ▶); Guthrie et al. (1981 ▶); Màrton-Merész et al. (1983 ▶); Biswas et al. (1996 ▶); Bai et al. (2004 ▶). For related literature, see: Li & Lowary (2008 ▶).

Experimental

Crystal data

C₃₃H₂₉N₇O₁₂
M _r = 715.63
Monoclinic,
a = 6.8522 (11) Å
b = 17.747 (3) Å
c = 13.729 (2) Å
β = 99.006 (2)°
V = 1648.9 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 193 (2) K
0.63 × 0.56 × 0.04 mm

Data collection

Bruker SMART 1000 CCD area-detector/PLATFORM diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.756, T _max = 0.996
13919 measured reflections
3905 independent reflections
3150 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.104
S = 1.04
3905 reflections
471 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT (Bruker, 2003 ▶); 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 global, III. DOI: 10.1107/S1600536808000718/bq2060sup1.cif

e-64-0o459-sup1.cif^{(28.9KB, cif)}

Structure factors: contains datablocks III. DOI: 10.1107/S1600536808000718/bq2060IIIsup2.hkl

e-64-0o459-IIIsup2.hkl^{(191.4KB, 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
N11—H11N⋯O10	0.88	2.00	2.618 (3)	126

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Acknowledgments

This work was supported by the Natural Sciences and Engineering Research Council of Canada, the Alberta Ingenuity Centre for Carbohydrate Science and the University of Alberta.

supplementary crystallographic information

Comment

As part of an ongoing program on the synthesis of furanose ring mimetics (Callam & Lowary, 2000; Callam & Lowary, 2001; Callam et al., 2001; Centrone & Lowary, 2002), we have endeavored to prepare compounds of the general structure (I). The route we developed for the preparation of these materials (Li & Lowary, 2008) started from an achiral starting material and relied upon a late stage resolution by derivatization with O-acetyl-(S)-mandelic acid. In the course of synthesizing (I), aldehyde (II) was prepared and, to determine the absolute configuration of the sterogenic centers in the cyclopentane ring, it was reacted with 2,4-dinitrophenylhydrazine to afford hydrazone derivative (III), which is a crystalline solid.

[Insert Scheme 1 here]

The structure of (III) in the crystal is shown in Fig. 1. The five-membered ring adopts an envelope conformation in which C3 is displaced below the plane formed by C1, C2, C4 and C5 and is therefore oriented cis to the fused cyclopropane moiety. Thus, the conformation of this ring is similar to that in other bicyclo[3.1.0]hexane analogues (examples: Gurskaya et al., 1990; Gurskaya et al., 1996; Gallucci et al., 2000; Garcia et al., 1992; Guthrie et al., 1981; Màrton-Merész, et al., 1983; Biswas et al., 1996; Bai et al., 2004). The absolute configuration of the stereogenic centers in the molecule could be established by comparison with those present in the (S)—O-acetylmandeloxyl substituents attached at C2 and C3. Thus, the absolute configuration was established as 1(R), 2(R), 3(R), 4(R), 5(S).

[Insert Figure 1 here]

Experimental

Compound (II) (5.8 mg, 0.011 mmol) was dissolved in CH₃OH (1 ml) and 1M 2,4-dinitrophenylhydrizine (1 ml) was added. The mixture was swirled for 1 min and then the solution was concentrated. The resulting residue was purified by chromatography (3:1 hexane-EtOAc) to give (III) (yield 4.2 mg, 53%) as a yellow solid. This material was recrystallized from CH₃OH to give a crystalline material (m.p. = 331–333 K).