7-Azido-N,N-diethyl-4,5-O-isopropyl­idene-4-C-methyl-3,6-anhydro-7-de­oxy-d-glycero-d-manno-heptonamide

Sarah F Jenkinson; Chen Wang; Maria-Soledad Pino-González; George W J Fleet; David J Watkin

doi:10.1107/S1600536808044279

. 2009 Jan 8;65(Pt 2):o263. doi: 10.1107/S1600536808044279

7-Azido-N,N-diethyl-4,5-O-isopropylidene-4-C-methyl-3,6-anhydro-7-deoxy-d-glycero-d-manno-heptonamide

Sarah F Jenkinson ^a,^*, Chen Wang ^a, Maria-Soledad Pino-González ^b, George W J Fleet ^a, David J Watkin ^c

PMCID: PMC2968166 PMID: 21581878

Abstract

The reaction of 5-azido-5-deoxy-2,3-O-isopropylidene-2-C-methyl-d-ribose with N,N-diethyl-2-(dimethylsulfuranylidene)acetamide gave the title compound, C₁₅H₂₆N₄O₅, as the major product arising from initial formation of an epoxide which was subsequently opened by intramolecular attack of the free 4-hydroxyl group. X-ray crystallography confirmed the relative stereochemistry of the title compound and the absolute configuration was determined by the use of d-ribose as the starting material. The crystal structure contains chains of molecules running parallel to the a axis, being linked by weak bifurcated O—H⋯(N,N) hydrogen bonds.

Related literature

For related literature see: Assiego et al. (2004 ▶); Pino-González et al. (2003 ▶, 2008 ▶); Valpuesta Fernández et al. (1990 ▶); Valpuesta et al. (1993 ▶); Görbitz (1999 ▶).

Experimental

Crystal data

C₁₅H₂₆N₄O₅
M _r = 342.40
Orthorhombic,
a = 8.64400 (10) Å
b = 13.4195 (2) Å
c = 15.9146 (3) Å
V = 1846.06 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 150 K
0.60 × 0.60 × 0.40 mm

Data collection

Area diffractometer
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.82, T _max = 0.96
23123 measured reflections
2354 independent reflections
2077 reflections with I > 2σ(I)
R _int = 0.077

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.129
S = 1.02
1992 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: COLLECT (Nonius, 2001 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: CAMERON (Watkin et al., 1996 ▶); software used to prepare material for publication: CRYSTALS.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808044279/lh2750sup1.cif

e-65-0o263-sup1.cif^{(18.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808044279/lh2750Isup2.hkl

e-65-0o263-Isup2.hkl^{(117.9KB, 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
O17—H171⋯N10ⁱ	0.88	2.30	3.112 (4)	152
O17—H171⋯N11ⁱ	0.88	2.45	3.313 (4)	167

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Symmetry code: (i) Inline graphic .

Acknowledgments

MSPG is grateful to Junta de Andalucia for a grant. The authors thank the Oxford University Crystallography Service for use of the instruments.

supplementary crystallographic information

Comment

The use of sulfur ylids in the stereoselective formation of epoxides and their subsequent regioselective opening has been utilized in the formation of iminosugars such as the seven-membered ring azepanes (Assiego et al., 2004), pipecolic acid derivatives (Pino-González et al.,2008) and piperidines (Pino-González et al., 2003). In order to extend this methodology the reaction of azido ribose derivative 1 with N,N-diethyl-2-(dimethylsulfuranylidene)acetamide was investigated.

Reaction of azido ribose derivative 1 with the sulfur ylid gave the title compound, furan 3, as the major product (Fig. 1). The product was confirmed, by both X-ray crystallography and the use of D-ribose as the starting material, to have the D-glycero-D-manno stereochemistry (Fig. 2) arising from initial attack of the ylid on the Si face of the aldehyde, as predicted from a Felkin-Ahn model (Valpuesta Fernández et al., 1990; Valpuesta et al., 1993), resulting in formation of epoxide 2, followed by intramolecular opening of the epoxide to give the title compound 3.

The compound was seen to adopt weakly (O—H···N) hydrogen bonded chains of molecules running parallel to the a-axis. The hydrogen bond is bifurcated (Fig. 3). Only classical hydrogen bonding has been considered.

Experimental

The title compound was recrystallized by vapour diffusion from a mixture of ethyl acetate and cyclohexane: m.p. 371–373 K; [α]_D²³ +16.4 (c, 1.0 in CHCl₃).