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

Alexandre Baralle; Shinya Otsuka; Vincent Guérin; Kei Murakami; Hideki Yorimitsu; Atsuhiro Osuka

doi:10.1055/s-0034-1378914

Synlett, Table of Contents

Synlett 2015; 26(03): 327-330
DOI: 10.1055/s-0034-1378914

cluster

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

Alexandre Baralle

^a Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan Fax: +81(75)7533970 Email: yori@kuchem.kyoto-u.ac.jp

,

Shinya Otsuka

^a Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan Fax: +81(75)7533970 Email: yori@kuchem.kyoto-u.ac.jp

,

Vincent Guérin

^a Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan Fax: +81(75)7533970 Email: yori@kuchem.kyoto-u.ac.jp

,

Kei Murakami

^a Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan Fax: +81(75)7533970 Email: yori@kuchem.kyoto-u.ac.jp

^b The Hakubi Center for Advanced Research, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan

,

Hideki Yorimitsu*

^a Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan Fax: +81(75)7533970 Email: yori@kuchem.kyoto-u.ac.jp

^c ACT-C, JST, Sakyo-ku, Kyoto 606-8502, Japan

,

Atsuhiro Osuka

^a Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan Fax: +81(75)7533970 Email: yori@kuchem.kyoto-u.ac.jp

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Abstract

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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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References

References and Notes

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8 Ni–NHC catalysts are known to be more effective than Ni–phosphine catalysts for cross-coupling arylation of organosulfur compounds with aryl Grignard reagents. See ref. 4b,g,h.

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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.
14 Malamas MS, Sredy J, Moxham C, Katz A, Xu W, McDevitt R, Adebayo FO, Sawicki DR, Seestaller L, Sullivan D, Taylor JR. J. Med. Chem. 2000; 43: 1293

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