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Sustainable Fe–ppm Pd nanoparticle catalysis of Suzuki-Miyaura cross-couplings in water

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Science  04 Sep 2015:
Vol. 349, Issue 6252, pp. 1087-1091
DOI: 10.1126/science.aac6936
  • Fig. 1 Ligand optimization for Fe–ppm Pd catalysis of Suzuki-Miyaura cross-couplings.

    Conditions were as follows: 4-bromoanisole (0.5 mmol), naphthalene-1-boronic acid (0.75 mmol), 5 mol % Fe–ppm Pd nanoparticles, K3PO4•H2O (0.75 mmol), 2 wt % TPGS-750-M (1 ml). Asterisks indicate yields based on gas chromatography–mass spectrometry (GC-MS).

  • Fig. 2 Couplings between aryl halides (Ar-X) and aryl (Ar') or alkenyl boron derivatives.

    Unless otherwise noted, conditions for these couplings were as follows: Ar-X (0.5 mmol), Ar'-BRn (0.6 mmol), FeCl3 (5 mol %), SPhos (5 mol %), MeMgCl (10 mol %), K3PO4•H2O (0.75 mmol), TPGS-750-M (2 wt %, 1 ml), 45°C. Room temperature, rt. Asterisks indicate the use of Ar-B(OH)2 or Ar-B(MIDA) (1.2 mmol) and K3PO4•H2O (1.5 mmol). Reported yields are for isolated, chromatographically purified materials. 320 ppm Pd is required (the general procedure is described in detail in the supplementary materials).

  • Fig. 3 Control reactions documenting the importance of both Fe and Pd in catalyst formation.

    Details are provided in the supplementary materials.

  • Fig. 4 Catalyst characterization.

    (A to C) Cryo-TEM images of Fe-Pd nanorods in aqueous TPGS-750-M. (D and E) SEM images of the solid nanomaterial. (F) AFM image of the solid nanomaterial.

  • Fig. 5 Further applications of Fe–ppm Pd–catalyzed couplings.

    (A) Sequential reactions, including a Suzuki-Miyaura coupling using Fe–ppm Pd nanoparticles as the catalyst (TMSI, TMS iodide; DIPEA, diisopropylethylamine; cBRIDP, di-t-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine; KO-t-Bu, potassium t-butoxide; TIPSOH, triisopropylsilyl alcohol). (B) A representative example suggestive of the extension of this approach to Sonogashira couplings (OTBS, t-butyldimethylsilyloxy).

Supplementary Materials

  • Sustainable Fe–ppm Pd nanoparticle catalysis of Suzuki-Miyaura cross-couplings in water

    Sachin Handa, Ye Wang, Fabrice Gallou, Bruce H. Lipshutz

    Materials/Methods, Supplementary Text, Tables, Figures, and/or References

    Download Supplement
    • Materials and Methods
    • Figs. S1 to S18
    • Tables S1 to S15

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