(6S*)-6-[(1S*,2R*)-1,2-Di­hydroxy­pent­yl]-4-meth­oxy-5,6-di­hydro-2H-pyran-2-one

Domenic J Valenti; Atta M Arif; Gary A Strobel; James K Harper

doi:10.1107/S1600536813027025

. 2013 Oct 19;69(Pt 11):o1657–o1658. doi: 10.1107/S1600536813027025

(6S)-6-[(1S,2R*)-1,2-Dihydroxypentyl]-4-methoxy-5,6-dihydro-2H-pyran-2-one

Domenic J Valenti ^a, Atta M Arif ^b, Gary A Strobel ^c, James K Harper ^a,^*

PMCID: PMC3884319 PMID: 24454095

Abstract

The title compound, C₁₁H₁₈O₅, was isolated from a liquid culture of Pestalotiopsis sp. In the molecule, the pyran-2-one ring assumes a half-chair conformation. The two terminal C atoms of the pentyl group were refined as disordered over two sets of sites, with refined occupancies of 0.881 (10) and 0.119 (10). In the crystal, molecules are linked via O—H⋯O hydrogen bonds forming a three-dimensional network.

Related literature

For the first isolation of the title compound, see: McGahren et al. (1973 ▶). For the natural and unnatural stereospecific synthesis, see: Kirihata et al. (1990 ▶, 1992a ▶,b ▶); Masaki et al. (1994 ▶). For closely related products from other fungi, see: Kimura et al. (1986 ▶); Kirihata et al. (1996 ▶); Lee et al. (1995 ▶); Davies-Coleman & Rivett (1989 ▶). For biological activity, see: Venkatasubbaiah & Van Dyke (1991 ▶). For crystal structures of related compounds, see: Yoshino & Nowacki (1972 ▶); Engel & Nowacki (1972a ▶,b ▶). graphic file with name e-69-o1657-scheme1.jpg

Experimental

Crystal data

C₁₁H₁₈O₅
M _r = 230.25
Orthorhombic,
a = 5.0375 (3) Å
b = 11.4515 (13) Å
c = 20.802 (2) Å
V = 1200.02 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 200 K
0.28 × 0.18 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997 ▶) T _min = 0.973, T _max = 0.992
2711 measured reflections
1616 independent reflections
1153 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.121
S = 1.06
1616 reflections
188 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: WinGX (Farrugia, 2012 ▶), ORTEP-3 for Windows (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813027025/lh5653sup1.cif

e-69-o1657-sup1.cif^{(25.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813027025/lh5653Isup2.hkl

e-69-o1657-Isup2.hkl^{(79.7KB, hkl)}

Click here for additional data file.^{(5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813027025/lh5653Isup3.cml

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′—H1′O⋯O2ⁱ	0.85 (3)	1.93 (3)	2.778 (3)	177 (3)
O2′—H2′O⋯O2′ⁱⁱ	0.80 (4)	2.05 (4)	2.8178 (18)	163 (4)

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Symmetry codes: (i) Inline graphic ; (ii) .

supplementary crystallographic information

1. Comment

The title compound was first isolated from an unidentified Penicillium sp. (McGahren et al., 1973). Multiple routes have been reported for the total synthesis (Kirihata et al., 1990; Kirihata et al., 1992a; Masaki et al., 1994) including syntheses creating unnatral stereoisomers (Kirihata et al., 1992b). Closely related products have been reported from other fungi (Kirihata et al., 1996; Lee et al., 1995). The 6-substituted 5,6-dihydropyran-2-one moiety present in the title compound is also found in natural products from several species of plants and fungi (Davies-Coleman & Rivett, 1989). Although many structures with this moiety exhibit bioactivity, it appears that the title compound displays none of the reported activities. Notably, the gibberellin synergistic activity of the very closely related compound pestalotin is not found (Kimura et al., 1986; Venkatasubbaiah & Van Dyke, 1991). In our lab we observed moderate antifungal activity. Crystal structures for the related natural products, kavain, dihydrokavain and methysticin have been reported (Yoshino & Nowacki, 1972; Engel & Nowacki, 1972a; Engel & Nowacki, 1972b). In the title compound, the atoms of the pyran-2-one assume a half-chair conformation. The conformations of the methoxy and dihydroxypentyl groups are shown in Fig. 1. Carbons 4' and 5' are disordered over two sites with occupancies of 0.881 (10):0.119 (10). In the crystal, molecules are linked via O—H···O hydrogen bonds forming a three-dimensional network (see Table 1 and Fig. 2).

2. Experimental

The title compound was obtained by liquid-liquid extraction (CH₂Cl₂/H₂O) of a culture of an endophytic Pestalotiopsis sp. The CH₂Cl₂ fraction was evaporated under reduced pressure then purified by chromatography on a silica column with CHCl₃/CH₃OH (8/2) as eluent. After pooling common fractions, a crystal was grown by slow evaporation of a MeOH solution.