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Synthesis 2010(2): 320-328  
DOI: 10.1055/s-0029-1217092
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

[5+3] Cycloaddition of 3-Oxidopyrylium: A Novel Route to Functionalized Cyclooctanoids from Furans

Urlam Murali Krishna*a,b, Mahendra P. Patila, Raghavan B. Sunoj*a, Girish K. Trivedia
a Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India
b Department of Surgery and Biomedical Engineering, Emory University, School of Medicine, Atlanta, GA 30322, USA
Fax: +1(404)7273660; e-Mail: murlam@emory.edu; e-Mail: sunoj@chem.iitb.ac.in;
Further Information

Publication History

Received 11 August 2009
Publication Date:
03 November 2009 (online)

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Abstract

We report a facile and efficient synthesis of highly functionalized cyclooctanoid derivatives by employing a dimerization reaction of 3-oxidopyrylium ylides. Different substituents are introduced on the dimer and the stereochemical outcome of the resultant cyclooctanoids is unambiguously established by single-crystal X-ray analysis.

Key words

cyclooctanoids - 3-oxidopyrylium ylides - [5+3] cycloadditions - stereoselectivity - density functional calculations

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15

CCDC 232578 (8), 232579 (11), and 735916 (17) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
X-ray crystallographic data for 8: CCDC 232578, empirical formula C12H16O5, formula weight 240.25, T = 293(2) K, λ = 0.70930 Å, crystal system monoclinic, space group P21/n, unit cell dimensions a = 7.4888(5) Å, α = 90.000˚, b = 15.2345(11) Å, β = 98.888(5)˚, c = 10.0221(5) Å, γ = 90.000˚, V = 1129.67(12) ų, Z = 4, D calcd = 1.413 Mg/m³, absorption coefficient 0.110 mm-¹, F(000) = 512, crystal size 0.35 × 0.30 × 0.20 mm, data collection θ range 2.45-25.01˚, index ranges 0 ≤ h ≤ 8, 0 ≤ k ≤ 18, -11 ≤ l ≤ 11, reflections collected 1875, unique 1875 [R(int) = 0.0000], refinement method full-matrix least-squares on F2, data/restraints/parameters 1875/0/220, goodness-of-fit on F ² 1.134, final R indices [I > 2σ(I)] R1 = 0.0539, wR2 = 0.1481, R indices (all data) R1 = 0.0571, wR2 = 0.1524, largest diff. peak and hole 0.249 and -0.394 e˙Å-³.
X-ray crystallographic data for 11: CCDC 232579, empirical formula C14H18O6, formula weight 282.28, T = 293(2) K, λ = 0.70930 Å, crystal system: monoclinic, space group P21/n, unit cell dimensions a = 10.5020(13) Å, b = 10.6560(10) Å, c = 12.9850(18) Å, β = 109.664(10)˚, V = 1368.4(3) ų, Z = 4, D calcd = 1.370 Mg/m³, absorption coefficient 0.107 mm-¹, F(000) = 600, crystal size 0.4 × 0.35 × 0.35 mm, data collection θ range 2.17-24.90˚, index ranges 0 ≤ h ≤ 12, 0 ≤ k ≤ 12, -15 ≤ l ≤ 14, reflections collected 1840, unique 1840 [R(int) = 0.0000], refinement method full-matrix least-squares on F2, data/restraints/parameters 1840/0/253, goodness-of-fit on F ² 1.023, final R indices [I > 2σ(I)] R1 = 0.0711, wR2 = 0.1712, R indices (all data) R1 = 0.0875, wR2 = 0.1823, largest diff. peak and hole 0.339 and -0.283 e˙Å-³.
X-ray crystallographic data for 17: CCDC 735916, empirical formula C25H28O4, formula weight 392.47, T = 293(2) K, λ = 0.70930 Å, crystal system monoclinic, space group P21/c, unit cell dimensions a = 7.550(5) Å, b = 24.686(3) Å, c = 11.4950(10) Å, β = 90.116(7)˚, V = 2087.1(3) ų, Z = 4, D calcd = 1.249 Mg/m³, absorption coefficient 0.083 mm-¹, F(000) = 840, crystal size 0.4 × 0.4 × 0.35 mm, data collection θ range 1.65-24.92˚, index ranges 0 ≤ h ≤ 8, 0 ≤ k ≤ 29, -13 ≤ l ≤ 13, reflections collected 3074, unique 3074 [R(int) = 0.0000], refinement method full-matrix least-squares on F2, data/restraints/parameters 3074/0/375, goodness-of-fit on F ² 1.065, final R indices [I > 2σ(I)] R1 = 0.0423, wR2 = 0.0983, R indices (all data) R1 = 0.0620, wR2 = 0.1107, largest diff. peak and hole 0.183 and -0.162 e˙Å-³.

21

This prediction is in accordance with experimental attempts for the ring closure in which starting material is recovered instead of the desired cyclic product.