Research ArticleChemistry

Ni-catalyzed deaminative cross-electrophile coupling of Katritzky salts with halides via C─N bond activation

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Science Advances  28 Jun 2019:
Vol. 5, no. 6, eaaw9516
DOI: 10.1126/sciadv.aaw9516
  • Fig. 1 Electrophiles for cross-coupling reactions.

    (A) Sources of alkyl electrophiles for radical cross-coupling reactions. RAE, redox-active esters. (B) Examples of redox-active Katritzky salts in recent years. (C) Optimization of deaminative cross-electrophile coupling with 1-a.

  • Fig. 2 Substrate scope of the reaction.

    aIsolated yields. bCondition A: Pyridinium salts (0.2 mmol), NiBr2•diglyme (0.02 mmol), L3 (0.02 mmol), zinc flake (−325 mesh, 99.9%) (0.5 mmol), aryl iodide 2 (0.3 mmol), and DMF (2.0 ml), 60°C. cCondition B: Pyridinium salts (0.2 mmol), Ni(acac)2 (0.02 mmol), L1 (0.02 mmol), zinc flake (−325 mesh, 99.9%) (0.5 mmol), bromoalkynes (0.3 mmol), and DMF (1.0 ml), 60°C. dCondition C: Pyridinium salts (0.2 mmol), Ni(COD)2 (0.04 mmol), L1 (0.04 mmol), tetrabutylammonium iodide (0.1 mmol), zinc flake (−325 mesh, 99.9%) (0.5 mmol), bromoalkanes (0.8 mmol), and dimethylamine (1.0 ml), 60°C.

  • Fig. 3 Synthesis of the precursor to the key lactonic moiety in (+)-compactin and (+)-mevinolin.

  • Fig. 4 Proposed mechanism of the Ni-catalyzed cross-coupling reaction.

Supplementary Materials

  • Supplementary Materials

    This PDF file includes:

    • Table S1. Optimization of cross-coupling with bromoalkynes.
    • Table S2. Optimization of cross-coupling with alkyl bromides.
    • Characterization data and NMR spectra of the cross-coupling products 2 to 35.

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    Files in this Data Supplement:

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