Oxidative Coupling of Alkylated Anisole Derivatives Using MoCl₅

Abstract

Despite the Lewis acidic character of MoCl₅ it can be employed for the selective oxidative coupling reaction of alkylated anisole derivatives without transalkylation or de-tert-butylation of the substrates. The spatial demand close to the donor function seems to be beneficial.

Key words

biaryls - coupling - dimerizations - anisole - molybdenum

References

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• Analytical data for known biaryls correspond to the literature:
• 11a

  See ref.¹⁶

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• 19a

  Data set was collected with Nonius KappaCCD diffractometer, equipped with a rotating anode generator Nonius FR591. Programs used: data collection COLLECT (Nonius B.V., 1998), data reduction Denzo-SMN,^19b absorption correction SORTAV,^19c,d structure solution SHELXS-97,^19e structure refinement SHELXL-97 (G. M. Sheldrick, Universität Göttingen, 1997), graphics VMD 1.8 (W. Humphrey, A. Dalke, K. Schulten, University of Illinois) and POV-ray 3.5

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17

X-ray crystal structure analysis for 1b: formula C₂₂H₃₀O₂, M = 326.46, colorless crystal 0.35 × 0.15 × 0.10 mm, a = 10.711 (1), b = 15.276 (1), c = 11.784 (1) Å, = 94.77 (1), V = 1921.4 (3) ų, ρ _calc = 1.129 g cm^-3, µ = 5.42 cm^-1, empirical absorption correction (0.833T0.948), Z = 4, monoclinic, space group C2/c (No. 15), λ = 1.54178 Å, T = 223 K, ω and φ scans, 5262 reflections collected (h, k, l), [(sinθ)/λ] = 0.59 Å^-1, 1568 independent (R _int = 0.041) and 1262 observed reflections [I2 σ(I)], 113 refined parameters, R = 0.042, wR ² = 0.124, max. residual electron density 0.14 (-0.13) e Å^-3, hydrogens calculated and refined as riding atoms.²⁰

18

X-ray crystal structure analysis for 6b: formula C₁₆H₁₄O₂, M = 238.27, light yellow crystal 0.50 × 0.40 × 0.05 mm, a = 5.799 (1), b = 12.856 (1), c = 7.673 (1) Å, = 98.54 (1), V = 565.7 (1) ų, ρ _calc = 1.399 g cm^-3, µ = 7.27 cm^-1, no absorption correction (0.713T0.965), Z = 2, monoclinic, space group P2₁/c (No. 14), λ = 1.54178 Å, T = 223 K, ω/2θ scans, 2469 reflections collected (-h, k, l), [(sinθ)/λ] = 0.62 Å^-1, 1152 independent (R _int = 0.042) and 1011 observed reflections [I2 σ(I)], 83 refined parameters, R = 0.047, wR ^² = 0.135, max. residual electron density 0.43 (-0.19) e Å^-3, hydrogens calculated and refined as riding atoms.

20

Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication CCDC-239234 and 239235. Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road, CambridgeCB2 1EZ, UK [fax: int. code [phone], e-mail: [e-mail]].