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.

biaryls - coupling - dimerizations - anisole - molybdenum

References

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All synthesized substrates were employed in analytically pure manner, their data correspond to the literature.

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Analytical data for known biaryls correspond to the literature:

11a

See ref.¹⁶

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11g

See ref.¹⁴

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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.

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

19b Otwinowski Z. Minor W. Methods Enzym.  1997,  276:  307 

19c Blessing RH. Acta Crystallogr., Sect. A  1995,  51:  33 

19d Blessing RH.
J. Appl. Cryst.  1997,  30:  421 

19e Sheldrick GM. Acta Crystallogr., Sect. A  1990,  46:  467 

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]].