3-O-Benzhydryl-2,5-dide­oxy-2,5-imino-2-C-methyl-l-lyxono-1,4-lactone

Filipa P da Cruz; K Victoria Booth; George W J Fleet; David J Watkin

doi:10.1107/S1600536808027888

. 2008 Sep 6;64(Pt 10):o1902–o1903. doi: 10.1107/S1600536808027888

3-O-Benzhydryl-2,5-dideoxy-2,5-imino-2-C-methyl-l-lyxono-1,4-lactone

Filipa P da Cruz ^a, K Victoria Booth ^a,^*, George W J Fleet ^a, David J Watkin ^b

PMCID: PMC2959362 PMID: 21201113

Abstract

The title bicyclic lactone, C₁₉H₁₉NO₃, is an intermediate in the synthesis of chiral α-methylprolines and branched C-methyl pyrrolidines; the absolute configuration was determined by the use of d-erythronolactone as the starting material. It exhibits no unusual crystal packing features, and each molecule acts as a donor and acceptor for one C—H⋯O hydrogen bond.

Related literature

For use of carbohydrates in synthesis see: Monneret & Florent (1994 ▶); Ireland et al. (1983 ▶); Hotchkiss et al. (2006 ▶, 2007a ▶,b ▶); Dukhan et al. (2005 ▶); Rao et al. (2008 ▶); Punzo et al. (2005a ▶,b ▶); Da Cruz et al. (2008 ▶). For related crystallographic literature see: Larson (1970 ▶); Prince (1982 ▶); Watkin (1994 ▶).

Experimental

Crystal data

C₁₉H₁₉NO₃
M _r = 309.36
Orthorhombic,
a = 9.0336 (2) Å
b = 10.0498 (2) Å
c = 17.5941 (4) Å
V = 1597.30 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 150 K
0.30 × 0.25 × 0.25 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.94, T _max = 0.98
25603 measured reflections
2071 independent reflections
1411 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.101
S = 0.86
2071 reflections
212 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: COLLECT (Nonius, 1997-2001 ▶).; 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 I. DOI: 10.1107/S1600536808027888/cs2089sup1.cif

e-64-o1902-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808027888/cs2089Isup2.hkl

e-64-o1902-Isup2.hkl^{(103.8KB, 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
C20—H201⋯O10ⁱ	0.93	2.36	3.293 (3)	174

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support (to FPC) provided by the Fundacao para a Ciencia e Tecnologia of Portugal is gratefully acknowledged. We also thank the Oxford University Crystallography Service for use of the instruments.

supplementary crystallographic information

Comment

Carbon-branched sugar lactones have hitherto been rarely used for the synthesis of enantiopure chiral targets (Monneret & Florent, 1994; Ireland et al., 1983). 2-C-Methyl-D-ribonolactone has become readily available in large amounts (Hotchkiss et al., 2007a) and has been used in the synthesis of branched α-C-nucleosides (Dukhan et al., 2005), 4-C-methylpentuloses (Rao et al., 2008) and branched imino sugars (Hotchkiss et al., 2007b). Derivatives of 2-C-methyl-D-arabinonolactone, such as 2, are accessible from D-erythronolactone 1 by addition of methyl magnesium bromide followed by further reaction with sodium cyanide (Hotchkiss et al., 2006; Punzo et al., 2005a). The tertiary alcohol 2 may be efficiently converted into the ribo-azide 3, the structure of which has been confirmed by X-ray crystallographic analysis (Da Cruz et al., 2008; Punzo et al., 2005b). The relative stereochemistry of 4 is firmly established in this paper by X-ray crystallographic analysis and the absolute configuration is defined by the use of D-erythronolactone 1 as the starting material.

The title compound exhibits no unusual crystal packing features. Each molecule acts as a donor and acceptor for one hydrogen bond, forming chains approximately parallel to the a-axis. A suggested hydrogen bond [N7 - H1 - O10] has been ignored in the packing diagram as it exceeds the limits of standard hydrogen bond length (2.52 Å)

Experimental

The title compound was recrystallized from cyclohexane and diethyl ether: m.p. 116–118°C; [α]_D²¹ -26.0 (c, 1.0 in MeCN).