rac-(3aR,6aR)-(E)-Methyl 2-(3a-methyl­perhydro­furo[3,2-b]furan-2-yl­idene)acetate

Lenka Bellovičová; Jozef Kožíšek; Jana Doháňošová; Angelika Lásiková; Tibor Gracza

doi:10.1107/S1600536810032101

. 2010 Aug 21;66(Pt 9):o2381. doi: 10.1107/S1600536810032101

rac-(3aR,6aR)-(E)-Methyl 2-(3a-methylperhydrofuro[3,2-b]furan-2-ylidene)acetate

Lenka Bellovičová ^a, Jozef Kožíšek ^a,^*, Jana Doháňošová ^b, Angelika Lásiková ^b, Tibor Gracza ^b

PMCID: PMC3007948 PMID: 21588718

Abstract

The constitution and relative configuration at the stereogenic centres and stereochemistry of the C—C double bond formed during Pd^II-catalysed domino reaction was established by X-ray analysis of the title compound, C₁₀H₁₄O₄. The asymmetric unit contains two molecules.

Related literature

The title compound was prepared from 4-methylpent-4-en-1,3-diol (Breit & Zahn, 2001 ▶) by a modified procedure for carbonylation of alkene-3-ol (Semmelhack & Epa, 1993 ▶).

Experimental

Crystal data

C₁₀H₁₄O₄
M _r = 198.21
Monoclinic,
a = 12.159 (1) Å
b = 5.8100 (3) Å
c = 28.509 (1) Å
β = 101.51 (1)°
V = 1973.5 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.84 × 0.36 × 0.12 mm

Data collection

Oxford Diffraction Gemini R CCD diffractometer
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2010 ▶); analytical numeric absorption correction using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995 ▶)] T _min = 0.941, T _max = 0.988
59312 measured reflections
4033 independent reflections
3571 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.091
S = 1.05
4025 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810032101/bv2142sup1.cif

e-66-o2381-sup1.cif^{(23.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032101/bv2142Isup2.hkl

e-66-o2381-Isup2.hkl^{(197.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Grant Agency of Slovak Republic, Grant Nos. VEGA 1/0817/08 and VEGA 1/0115/10, and the Structural Funds, Interreg IIIA, for financial support in purchasing the diffractometer.

supplementary crystallographic information

Comment

As a part of our long term program directed towards the application of palladium(II)-catalysed oxycarbonylation of unsaturated polyols in the natural product synthesis we studied the domino Pd(II)-promoted reactions. The title compound, [(I): alternative name: (±)-(1'R, 5'R)-(E)-methyl 2-(5'-methyl-2',6'-dioxabicyclo[3.3.0]octa-3'-ylidene) acetate] represents a product of the first diastereoselective domino intramolecular Wacker-type cyclization - Heck reaction - cyclization of 4-methylpent-4-en-1,3-diol with methyl acrylate. The asymmetric unit contains two molecules of the same chirality (Z' = 2), but as the space group is centrosymmetric, both enantiomers are present in the unit cell.

Experimental

The title compound was prepared from 4-methylpent-4-en-1,3-diol (Breit and Zahn, 2001) by a modified procedure for carbonylation of alkene-3-ol (Semmelhack and Epa, 1993). A mixture of 4-methylpent-4-en-1,3-diol (200 mg, 1.70 mmol, 1 equivalent) and CuCl freshly recrystallized (170 mg, 1.70 mmol, 1 equivalent) in dry DMF (7 ml) was stirred at r.t for 10 min. under oxygen atmosphere (balloon). The methyl acrylate (0.8 ml, 8.60 mmol, 5 equivalents) and palladium acetate (39 mg, 0.17 mmol, 0.1 equivalent) were then added. The mixture was stirred for 56 h, then diluted by ethyl acetate (100 ml). The organic solution was washed three times with sat. aq. ammonium chloride solution, driedover anhydrous magnesium sulfate, and concentrated in vacuo. The residue was purified by flash chromatography (SiO₂, ethyl acetate-hexane-3:1, Rf 0.73). The title compound was slowly crystallized from hexane to give white crystals [m.p. 65–67 °C].¹H NMR (300 MHz, Varian, CDCl₃): δ(p.p.m.) = 1.43 (s, 3H, CH₃); 2.17 (m, 2H, H-8'); 2.96 3.64 (2xd, 2H, J=19.7, H-4'); 3.69–4.04 (m, 6H, H-1', H-7', OCH₃); 4.66 (d, 1H, J= 6.3 Hz, H-2). ¹³C NMR (75 MHz, CDCl₃): δ(p.p.m.) = 22.7 (q, CH₃), 32.7 (t, C-8'), 44.2 (t, C-4'), 50.8 (q, OCH₃), 66.9 (t, C-7'), 87.7 (s, C-5'), 89.9 (d, C-1'), 91.3 (d, C-2), 168.7 (s, C-1), 175.7 (d, C-3'). IČ, film: ν(cm^-1) = 3479 (w), 2975 (m), 2951 (m), 2874 (w), 1789 (w), 1705 (s), 1645 (s), 1437 (s), 1410 (w), 1364 (s), 1317 (m), 1274 (m), 1193 (s), 1148 (s), 1106 (s), 1093 (s), 1039 (s), 1010 (m), 978 (m), 950 (w), 933 (w), 900 (w), 871 (w), 822 (m), 734 (w), 592 (w) [cm^-1]