2,3-O-(S)-Benzyl­idene-2-C-methyl-d-ribono-1,4-lactone

K Victoria Booth; Sarah F Jenkinson; George W J Fleet; David J Watkin

doi:10.1107/S1600536809032796

. 2009 Aug 22;65(Pt 9):o2199. doi: 10.1107/S1600536809032796

2,3-O-(S)-Benzylidene-2-C-methyl-d-ribono-1,4-lactone

K Victoria Booth ^a,^*, Sarah F Jenkinson ^a, George W J Fleet ^a, David J Watkin ^b

PMCID: PMC2969893 PMID: 21577602

Abstract

The crystal structure of the title compound, C₁₃H₁₄O₅, establishes (i) the (S) – rather than (R) – configuration at the acetal carbon and (ii) that both the acetal and the lactone form five- rather than six-membered rings; the absolute configuration is determined by the use of 2-C-methyl-d-ribono-1,4-lactone as the starting material. The compound consists of hydrogen-bonded chains of molecules running along the a axis; there are no unusual packing features. Only classical hydrogen bonding has been considered.

Related literature

For the synthesis of sugar lactones and their use as building blocks, see: Lundt & Madsen (2001 ▶); Hotchkiss, Soengas et al. (2007 ▶); Booth et al. (2008 ▶, 2009 ▶); Jenkinson et al. (2007 ▶); Hotchkiss, Kato et al. (2007 ▶); Chen & Joullie (1984 ▶); Dho et al. (1986 ▶); Baird et al. (1987 ▶). For the structures of benzylidene acetals, see: Baggett et al. (1985 ▶); Zinner et al. (1968 ▶).

Experimental

Crystal data

C₁₃H₁₄O₅
M _r = 250.25
Orthorhombic,
a = 8.6170 (2) Å
b = 10.4615 (3) Å
c = 13.2693 (5) Å
V = 1196.18 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 150 K
0.50 × 0.40 × 0.40 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.91, T _max = 0.96
8306 measured reflections
1547 independent reflections
1369 reflections with I > 2.0σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.075
S = 0.96
1547 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.18 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 global, I. DOI: 10.1107/S1600536809032796/lh2882sup1.cif

e-65-o2199-sup1.cif^{(15.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809032796/lh2882Isup2.hkl

e-65-o2199-Isup2.hkl^{(77.7KB, 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
O18—H181⋯O9ⁱ	0.84	2.02	2.801 (3)	153

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

We would like to thank the Chemical Crystallography Department and ALT at Oxford University for use of the difractometers.

supplementary crystallographic information

Comment

Lactones have been widely used for the enantiospecific synthesis of complex chiral targets (Lundt & Madsen, 2001). 2-C-Methyl-D-ribono-1,4-lactone 3 (Fig. 1) has recently become a readily available starting material (Hotchkiss, Soengas et al., 2007; Booth et al., 2008) and has been used in the synthesis of doubly branched sugars (Booth et al., 2009), 2-C-methyl nucleosides (Jenkinson et al., 2007) and complex piperidines (Hotchkiss, Kato et al., 2007). D-Ribono-1,4-lactone 5 with benzaldehyde and concentrated aqueous hydrochloric acid forms a 5 ring benzylidene acetal - 6-ring lactone 6 (Fig. 1). The structure of 6 was established by X-ray crystallographic analysis (Baggett et al., 1985) which corrected the original erroneous 6 ring benzylidene acetal - 5-ring lactone structure proposed (Zinner et al., 1968). The protected 1,5-lactone 6 leaves only the C-2 OH unprotected and has been widely used as a chiron (Chen & Joullie, 1984; Dho et al., 1986; Baird et al., 1987). It was hoped that the analogous reaction with 2-C-methyl lactone 3 would form the analogous lactone 4; however, treatment of 3 with benzaldehyde and concentrated aqueous hydrochloric acid gave as the major product a mixture of epimeric 1,4-lactones 1 and 2; although it was not possible to separate 1 and 2 by chromatography, suitable crystals of the major component 1 were obtained and the structure of a 5 ring benzylidene acetal - 5-ring lactone, together with the (S) stereochemistry at the acetal carbon, was firmly established (Fig. 2).

The compound consists of H—O···H hydrogen bonded chains of molecules running along the a-axis (Fig. 3); there are no unusual packing features. Only classical hydrogen bonding has been considered.

Experimental

The title compound was recrystallized from a mixture of diethyl ether and petrol by slow evaporation: m.p. 369–372 K; [α]_D¹⁸ -38.7 (c, 0.86 in CHCl₃).