(4R)-4-(2-Allyl-2H-1,2,3-triazol-4-yl)-1,2-O-isopropyl­idene-l-threose

Sarah F Jenkinson; Daniel Best; Francis X Wilson; George W J Fleet; David J Watkin

doi:10.1107/S1600536808036416

. 2008 Nov 13;64(Pt 12):o2361. doi: 10.1107/S1600536808036416

(4R)-4-(2-Allyl-2H-1,2,3-triazol-4-yl)-1,2-O-isopropylidene-l-threose

Sarah F Jenkinson ^a,^*, Daniel Best ^a, Francis X Wilson ^b, George W J Fleet ^a, David J Watkin ^c

PMCID: PMC2959937 PMID: 21581334

Abstract

X-ray crystallography unequivocally confirmed the structure of the title compound, C₁₂H₁₇N₃O₄, as (4R)-4-(2-allyl-2H-1,2,3-triazol-4-yl)-1,2-O-isopropylidene-l-threose. The absolute configuration was determined by the use of d-glucorono-3,6-lactone as the starting material. The crystal structure consists of hydrogen-bonded chains of molecules running parallel to the a axis. There are no unusual packing features.

Related literature

For related background information on the biotechnological interconversion of monosaccharides and other sugars, see: Izumori (2002 ▶, 2006 ▶); Granstrom et al. (2004 ▶); Yoshihara et al. (2008 ▶); Booth et al. (2008 ▶); Jenkinson, Booth, Gullapalli et al. (2008 ▶); Jenkinson, Booth, Yoshihara et al. (2008 ▶); Gullapalli et al. (2007 ▶); Jenkinson, Booth, Best et al. (2008 ▶). For related literature, see: Görbitz (1999 ▶).

Experimental

Crystal data

C₁₂H₁₇N₃O₄
M _r = 267.28
Orthorhombic,
a = 5.3959 (2) Å
b = 9.6233 (3) Å
c = 25.4532 (9) Å
V = 1321.69 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 150 K
0.30 × 0.20 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.82, T _max = 1.00 (expected range = 0.817–0.997)
9466 measured reflections
1528 independent reflections
1194 reflections with I > 2σ(I)
R _int = 0.096

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.098
S = 0.93
1528 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.33 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/S1600536808036416/lh2725sup1.cif

e-64-o2361-sup1.cif^{(15.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808036416/lh2725Isup2.hkl

e-64-o2361-Isup2.hkl^{(76.8KB, 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
O11—H111⋯O8ⁱ	0.88	1.95	2.822 (4)	170

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Symmetry code: (i) Inline graphic .

Acknowledgments

We thank the Oxford University Crystallography Service for access to equipment.

supplementary crystallographic information

Comment

The process for the biotechnological interconversion of monosaccharides developed by Izumori (Izumori, 2002; Izumori, 2006; Granstrom et al., 2004), has been seen to be generally applicable to other sugar derivatives such as 1-deoxy sugars (Yoshihara et al., 2008; Booth et al. 2008; Jenkinson, Booth, Gullapalli et al., 2008; Jenkinson, Booth, Yoshihara et al., 2008; Gullapalli et al., 2007). To evaluate the applicability of this process to 2-deoxy sugars and their derivatives a variety of carbon chain extension reactions were investigated, for example, addition of lithium tert-butyl acetate to sugar lactones (Jenkinson, Booth, Best et al., 2008) or addition of allyl magnesium bromide to an aldose.

Reaction of lactol 1 (Fig. 1) with 2.5 equivalents of allyl magnesium bromide generated a single isolable product along with recovered starting material. X-ray crystallography identified the compound as 4R-4-(2-allyl-2H-1,2,3-triazole-4-yl)-1,2-O-isopropylidene-L-threose 2 (Fig. 2) rather than the anticipated addition product 3. The crystal structure was seen to consist of alternating chains of hydrogen-bonded molecules running parallel to the a-axis (Fig. 3).Only classic intermolecular hydrogen bonding has been considered. The absolute configuration was determined from the starting material.

Experimental

The title compound was recrystallized by vapour diffusion from a mixture of diethyl ether and cyclohexane: m.p. 361–364 K; [α]_D²⁵ -13.9 (c, 0.69 in CHCl₃).