2-N-Benzyl-2,6-dide­oxy-2,6-imino-3,4-O-isopropyl­idene-3-C-methyl-d-allono­nitrile

Benjamin J Ayers; Sarah F Jenkinson; George W J Fleet; Amber L Thompson

doi:10.1107/S1600536812016273

. 2012 Apr 21;68(Pt 5):o1474. doi: 10.1107/S1600536812016273

2-N-Benzyl-2,6-dideoxy-2,6-imino-3,4-O-isopropylidene-3-C-methyl-d-allononitrile

Benjamin J Ayers ^a, Sarah F Jenkinson ^a,^*, George W J Fleet ^a, Amber L Thompson ^b

PMCID: PMC3344585 PMID: 22590347

Abstract

X-ray crystallography firmly established the relative stereochemistry of the title compound, C₁₇H₂₂N₂O₃. The absolute configuration was determined by use of 2-C-methyl-d-ribonolactone as the starting material. The compound exists as O—H⋯N hydrogen-bonded chains of molecules running parallel to the a-axis.

Related literature

For 2-C-methyl sugar lactones and their use in synthesis, see: da Cruz et al. (2011 ▶); Best et al. (2010 ▶); da Cruz & Horne (2008 ▶6); Booth et al. (2008 ▶); Hotchkiss, Soengas et al. (2007 ▶); Hotchkiss, Kato et al. (2007 ▶); Hotchkiss et al. (2006 ▶); Sowden & Strobach (1960 ▶). For the biological activity of polyhydroxylated piperidines, see: Nash et al. (2011 ▶); Watson et al. (2001 ▶). For the extinction correction, see: Larson (1970 ▶). For the temperature controller, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₇H₂₂N₂O₃
M _r = 302.37
Orthorhombic,
a = 8.5647 (3) Å
b = 10.0019 (4) Å
c = 18.7031 (7) Å
V = 1602.17 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 150 K
0.25 × 0.25 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.96, T _max = 0.98
7953 measured reflections
2082 independent reflections
1808 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.106
S = 0.97
2082 reflections
200 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 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 datablock(s) global, I. DOI: 10.1107/S1600536812016273/lh5456sup1.cif

e-68-o1474-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812016273/lh5456Isup2.hkl

e-68-o1474-Isup2.hkl^{(104.4KB, 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
O1—H11⋯N4ⁱ	0.88	2.15	2.997 (3)	161

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

Many polyhydroxylated piperidines have been found to display interesting biological properties (Nash et al., 2011; Watson et al., 2001). 2-C-Methyl lactones, derived from sugars (Hotchkiss, Soengas et al., 2007; Sowden & Strobach, 1960; Hotchkiss et al., 2006), have been used for the synthesis of iminosugars bearing a carbon branch (da Cruz et al., 2011; Best et al., 2010; da Cruz et al., 2008; Hotchkiss, Kato et al., 2007). In a new one-pot approach to carbon-branched piperidines, the α-iminonitrile 4 was prepared from the lactol tosylate 3, itself readily available in two steps from 2-C-methyl-D-ribonolactone 1 (Booth et al., 2008), by Strecker α-aminonitrile formation and concomitant intramolecular tosylate displacement (Fig. 1).

X-ray crystallography firmly established the relative stereochemistry of the title compound 4. The absolute configuration was determined by the use of 2-C-methyl-D-ribonolactone 1 as the starting material. The acetonide ring adopts an envelope conformation with C16 out of the plane and the piperidine ring adopts a chair conformation (Fig. 2). The compound exists as O—H···N hydrogen-bonded chains of molecules running parallel to the a-axis (Fig. 3). Only classical hydrogen-bonding was considered.

Experimental

α-Iminonitrile 4 was recrystallized by diffusion from a mixture of ethyl acetate and cyclohexane: m.p. 394–395 K; [α]_D²⁰ +39.7 (c 5.5, methanol).