Room-Temperature Stille Coupling of Tetraarylstannanes via Palladium-Catalyzed C–H Activation

Abstract

An effective room-temperature Stille cross-coupling of aryl ureas with tetraarylstannanes via palladium-catalyzed C–H bond activation is reported, providing a mild method for direct arylation of aromatic C–H bonds.

Key words

palladium - room temperature - Stille coupling - tetra­arylstannanes - C–H activation

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• 15 General Procedure for Stille Coupling of Tetraarylstannanes with Ureas Aryl urea 1 (0.2 mmol), aryl tin 2 (0.1 mmol), 1,4-benzoquinone (0.6 mmol), camphor sulfonic acid (1.0 mmol), and Pd(MeCN)₂(OTs)₂ (0.02 mmol) were sequen-tially added in air to a reaction tube equipped with a stir bar. AcOH (1.0 mL) was added by syringe, and the resulting mixture was vigorously stirred for 24 h at r.t. The reaction was then quenched with aq NaOH and extracted with EtOAc. The solution was dried with anhyd Na₂SO₄, filtered through a plug of silica gel, and then concentrated by rotary evaporation. The residue was purified by flash chroma-tography, eluting with PE–EtOAc to afford the products. N,N-Dimethyl-N′-(2-phenyl-4-methyl)phenyl Urea (3ba) Yield 80%; mp 135.8–136.4 °C, white powder. ¹H NMR (300 MHz, CDCl₃): δ = 7.94 (d, J = 7.9 Hz, 1 H), 7.38–7.31 (m, 5 H), 7.09 (d, J = 7.9 Hz, 1 H), 6.94 (s, 1 H), 6.33 (s, 1 H), 2.72 (s, 6 H), 2.25 (s, 3 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 155.6, 138.9, 134.2, 132.1, 131.7, 130.7, 130.4, 129.4, 128.9, 128.7, 127.4, 127.1, 120.7, 36.1, 20.6 ppm. IR (KBr): ν = 3447, 2920, 1642, 1567 cm^–1. ESI-HRMS: m/z calcd for C₁₆H₁₈N₂ONa [M + Na⁺]: 277.1317; found: 277.1310. N,N-Dimethyl-N′-(2-phenyl-4-trifluoromethoxy)phenyl Urea (3ha) Yield 46%; mp 145.5–146.3 °C, white powder. ¹H NMR (300 MHz, CDCl₃): δ = 8.13 (d, J = 9.0 Hz, 1 H), 7.43–7.32 (m, 5 H), 7.30 (d, J = 9.0 Hz, 1 H), 7.00 (s, 1 H), 6.43 (s, 1 H), 2.73 (s, 6 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 155.5, 144.1, 137.2, 135.3, 132.6, 129.3, 129.1, 128.7, 128.5, 122.2, 121.9, 121.3, 119.0, 36.1, 29.7 ppm. IR (KBr): ν = 3280, 2920, 1640, 1500 cm^–1. ESI-HRMS: m/z calcd for C₁₆H₁₅N₂O₂F₃Na [M + Na⁺]: 347.0983; found: 347.0982.