Trichodermol (4α-hydr­oxy-12,13-epoxy­trichothec-9-ene)

Jing-Li Cheng; Yong Zhou; Fu-Cheng Lin; Jin-Hao Zhao; Guo-Nian Zhu

doi:10.1107/S1600536809044080

. 2009 Oct 28;65(Pt 11):o2879. doi: 10.1107/S1600536809044080

Trichodermol (4α-hydroxy-12,13-epoxytrichothec-9-ene)

Jing-Li Cheng ^a, Yong Zhou ^a, Fu-Cheng Lin ^b, Jin-Hao Zhao ^a,^*, Guo-Nian Zhu ^a

PMCID: PMC2971347 PMID: 21578465

Abstract

In the title compound, C₁₅H₂₂O₃, the five-membered ring displays an envelope conformation, whereas the two six-membered rings show different conformations, viz. chair and half-chair. In the crystal, molecules are linked through intermolecular O—H⋯O hydrogen bonds, forming chains running along the b axis.

Related literature

For the fungicidal activity of the endophytic fungus Trichoderma taxi sp. nov. from Taxus mairei, see: Nielsen et al. (2005 ▶); Zhang et al. (2007 ▶). For the related Trichodermin structure, see: Chen et al. (2008 ▶). For the extinction correction, see: Larson (1970 ▶).

Experimental

Crystal data

C₁₅H₂₂O₃
M _r = 250.34
Monoclinic,
a = 6.8284 (2) Å
b = 6.6209 (3) Å
c = 14.7170 (6) Å
β = 96.7507 (11)°
V = 660.74 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.66 × 0.49 × 0.28 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.934, T _max = 0.976
6503 measured reflections
1634 independent reflections
1540 reflections with F ² > 2σ(F ²)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.095
S = 1.00
1634 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1993 ▶); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809044080/si2217sup1.cif

e-65-o2879-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809044080/si2217Isup2.hkl

e-65-o2879-Isup2.hkl^{(80.5KB, 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
O2—H201⋯O1ⁱ	0.84	2.02	2.839 (2)	165

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Symmetry code: (i) Inline graphic .

Acknowledgments

The work was supported by the Science and Technology Project of Zhejiang Province (No. 2008 C02007–3) and the National Natural Science Foundation of China (No. 30700532).

supplementary crystallographic information

Comment

The endophytic fungi Trichoderma taxi sp. nov. from Taxus mairei can produce a compound with fungicidal activity-Trichodermin (Zhang et al., 2007), which is a member of the 4β-aceoxy-12,13-epoxytrichothecene family (Nielsen et al., 2005). Bioassays showed Trichodermin strongly inhibited Rhizoctonia solani and Botrytis cinere. In order to find the relationship between the stereochemistry of the C4 position and biological activities, the title compound had been designed and synthesized. Its molecular structure is shown in Fig. 1. In the molecule, the five membered ring displays an envelope conformation with atom C11 at the flap position 0.715 (3) Å out of the mean plane formed by the other four atoms. The O1-containing six-membered ring displays a chair conformation. The typical C2=C3 double bond length of 1.325 (2) Å suggests that C2 and C3 atoms are sp² hybridized, which correlates with the larger C1—C2—C3 bond angle of 124.36 (16) ° and C2—C3—C4 bond angle of 122.95 (18) ° and a small C1—C2—C3—C4 torsion angle of -3.0 (3) °, as compared to 3.0 (3) ° in the compound of Trichodermin. And the C3-containing six-membered ring displays a half-chair conformation, as well as the compound of Trichodermin (Chen et al.). There are intermolecular O—H···O hydrogen bonds (Table 1) in the crystal structure, which lead to the formation of chains running along the b axis (Fig. 2).

Experimental

To a solution of 12,13-Epoxytrichothec-9-ene-4-one (1 g) in THF(100 ml) containing 10 ml of methanol was added sodium borohydride (100 mg) and the reactant was partitioned between 100 ml of ethyl acetate and water. The organic layer was dried with MgSO₄ and concentrated, and the residue was chromatographed to give 620 mg solid precipitate. The solid was filtrated and recrystallized with 95% ethanol to colourless blocks.

[α]D = 65.7 (c 0.052). ESI-MS: 251 (M+H)+ (100%); 1H-NMR (500 MHz, CDCl3, ppm): 5.46 (1H, d, J=5.5Hz, H-10), 4.27 (1H, t, H-4), 4.22 (1H, d, J=5.5Hz, H-2), 3.67 (1H, d, J=5.5Hz, H-11), 3.05 (1H, d, J=4.0Hz, H-13), 2.78 (1H, d, J=4.0Hz, H-13), 2.56-2.49 (1H, m, H-3), 2.00-1.97 (2H, m, H-8), 1.97-1.96 (1H, m, H-3), 1.96-1.94 (1H, m, H-7), 1.71 (3H, s, H-16), 1.33-1.31 (1H, m, H-7), 1.09 (3H, s, H-14), 0.86 (3H, s, H-15).