Nickel-Catalyzed Negishi-Type Arylation of Trialkylsulfonium Salts

Abstract

Negishi-type arylation of trialkylsulfonium salts with arylzinc reagents has been accomplished under nickel catalysis. The use of cyclohexanethiol as an additional ligand was found to be particularly important to promote C–S cleavage. The present reaction accommodates one-pot arylation of dialkyl sulfides by combining with S-methylation with MeOTf. Mechanistic experiments suggest that C–S cleavage would proceed via single-electron transfer (SET) to generate the most stable carbon-centered radical and that the thiolate ligand would promote the C–S cleavage and radical recombination step.

Key words

Negishi coupling - trialkylsulfonium salt - nickel catalysis - thiolate ligand - radical

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• 18 Ethyl 6-(4-Methoxyphenyl)hexanoate (3ba) Colorless oil (76 mg, 0.30 mmol, 60%). ¹H NMR (594 MHz): δ = 7.08 (d, J = 8.8 Hz, 2 H), 6.82 (d, J = 8.8 Hz, 2 H), 4.12 (q, J = 7.3 Hz, 2 H), 3.79 (s, 3 H), 2.55 (t, J = 7.5 Hz, 2 H), 2.28 (t, J = 7.5 Hz, 2 H), 1.68–1.57 (m, 4 H), 1.38–1.33 (m, 2 H), 1.25 (t, J = 7.3 Hz, 3 H). ¹³C NMR (149 MHz): δ = 174.0, 157.8, 134.8, 129.4, 113.8, 60.3, 55.4, 34.9, 34.4, 31.5, 28.8, 25.0, 14.4. HRMS (APCI-MS, positive): m/z calcd for C₁₅H₂₃O₃: 251.1642 [M + H]⁺; found: 251.1645.
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