Synthesis of Tetraarylallenes via Palladium-Catalyzed Addition-Elimination Reactions of 1,1,3-Triaryl-2-propyn-1-ols with Aryl Iodides

Abstract

The palladium-catalyzed reactions of tert-propargylic alcohols with aryl iodides afforded tetraarylallenes in good yields. This reaction involves: (1) oxidative addition of the aryl iodide to Pd(0); (2) arylpalladium intermediate coordination to the carbon-carbon triple bond of the 1,1,3-triaryl-2-propyn-1-ol and subsequent regioselective insertion of the alkynol to form β-hydroxyvinylpalladium species; and (3) β-elimination to produce the tetraarylallenes. Generally, the best results are obtained by employing 5 mol% of Pd(TFA)₂, 10 mol% of PPh₃, two equivalents of aryl iodide and five equivalents of Et₃N in MeCN.

Key words

palladium - tetraarylallenes - addition-elimination - 1,1,3-triaryl-2-propyn-1-ol

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23

Crystal data for 3aa: C₂₇H₂₀, M = 344.43 g/mol, crystal size: 0.50 × 0.50 × 0.50 mm, monoclinic, space group P2₁/c, λ = 0.71073 Å, a = 12.1405 (1) Å, b = 8.4186 (1) Å, c = 19.2201 (2) Å, α = 90°, β = 101.0624 (5)°, γ = 90°, V = 1927.91 (3) ų, Z = 4, D = 1.187 mg/m³, µ = 0.067
mm^-1, T = 295 (2) K, θ range: 1.71-27.50°, reflections collected: 17949, independent reflections: 4403 (R _int = 0.0313), refinement method: full-matrix least-squares on F², final R values [I > 2σ(I)]: R ₁ = 0.0516, wR ₂ = 0.1300. Diffractometer: NONIUS KappaCCD. Crystallographic data (excluding structure factors) for this structure have been deposited at the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 260843, and may be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1ED, UK [fax: [phone];
e-mail [e-mail]].