Nickel–NHC-Catalyzed Cross-Coupling of 2-Methylsulfanylbenzofurans with Alkyl Grignard Reagents

Abstract

NiCl₂(PPh₃)(IPr) catalyzes cross-coupling reactions of 2-methylsulfanylbenzofurans with alkyl Grignard reagents. Other nickel complexes such as NiCl₂(dppe) failed to catalyze the same reaction. The alkylation is applicable to the synthesis of a couple of protein tyrosine phosphatase inhibitors, 3-(4-biphenylyl)-2-alkylbenzofurans.

Key words

nickel - alkylation - cross-coupling - sulfide - homogeneous catalysis

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• 12 Butylation of 1a – Representative ProcedureNiCl₂(PPh₃)(IPr) (11.7 mg, 0.015 mmol) was placed in a dry Schlenk tube equipped with a magnetic stir bar and a rubber septum under argon. A solution of methylsulfanylbenzofuran (1a, 120 mg, 0.50 mmol) in THF (5.0 mL) was then added. Butylmagnesium bromide (0.60 M in THF, 1.0 mL, 0.60 mmol) was then added to the mixture, and the resulting mixture was stirred for 30 min at 25 °C. The mixture was filtered through a pad of silica gel with copious washings with CH₂Cl₂. The filtrate was evaporated to leave a crude oil. ¹H NMR analysis of the oil revealed the yield of 2a was quantitative. Silica gel column purification (n-hexane) afforded butylated benzofuran 2a (121 mg, 0.48 mmol) in 97% yield as a colorless oil.2-Butyl-3-phenylbenzo[b]furan (2a) ¹H NMR (600 MHz, CDCl₃): δ = 7.60 (d, 1 H, J = 7.8 Hz), 7.54–7.50 (m, 5 H), 7.40 (t, 1 H, J = 6.6 Hz), 7.30 (t, 1 H, J = 6.6 Hz), 7.25 (t, 1 H, J = 7.8 Hz), 2.90 (t, 2 H, J = 7.8 Hz), 1.81 (quint, 2 H, J = 7.2 Hz), 1.44 (sext, 2 H, J = 7.2 Hz), 0.95 (t, 3 H, J = 7.2 Hz) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 155.46, 154.18, 133.07, 129.25, 129.06, 128.86, 127.12, 123.66, 122.68, 119.57, 116.93, 110.97, 30.68, 26.66, 22.61, 13.95 ppm. IR: 2956, 2928, 2871, 1610, 1496, 1454, 1255, 1219, 1174, 1012, 969, 769, 700 cm^–1. ESI-HRMS: m/z calcd for C₁₈H₁₈OH [M + H]⁺: 281.1536; found: 281.1538.
• 13 The scope of benzofuran substrates in the alkylation seems to be narrower than that in our previous arylation at present. For instance, 3-CF₃-substituted benzofuran resisted the butylation whereas it underwent smooth arylation in ref. 6f.
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