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Figures of the Article
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State-of-the-art aromatic amine synthesis and our strategy. DG = directing group; FG = functional group; DEMS = diethoxymethylsilane; diglyme = 2-methoxyethyl ether; TBAI = tetrabutylammonium iodide.
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Scope of substrates. Standard conditions: nitroarene (0.20 mmol, 1.0 equiv.), alkene (0.40 mmol, 2.0 equiv.), NiBr2(diglyme) (0.02 mmol, 10 mol%), L8 (0.03 mmol, 15 mol%), DEMS (2.0 mmol, 10.0 equiv.), Na2CO3 (0.60 mmol, 3.0 equiv.), TBAI (0.10 mmol, 0.5 equiv.), Mg powder (0.10 mmol, 0.5 equiv.), solvent (1,4-dioxane∶MeOH = 5∶1, 1.20 mL, 0.167 mol/L), 50 °C, 12 h. The yield represents the isolated yield of the major product. The reaction regioselectivity was determined by GC analysis of the reaction mixture. aFor these cases, the reaction regioselectivity could not be determined by GC analysis, 1H NMR determined regioisomeric ratios shown in the table after chromatography purification. bL1 instead of L8 as ligand. DEMS = Diethoxymethylsilane; TBAI = Tetrabutylammonium iodide.
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Synthetic applications. Standard conditions are shown in Fig. 2. aThe yield represents the total GC yield. The reaction regioselectivity was determined by GC analysis of the reaction mixture. bThe yield represents the isolated yield of the major product. The reaction regioselectivity was determined by GC analysis of the reaction mixture. cYields reported in reference. dThe yield represents the isolated yield of the major product. Regioselectivity could not be determined by GC analysis. The regioisomeric ratio was determined to be >20∶1.0 l∶b by 1H NMR after chromatography purification. DCMI-PHOS = dicyclohexyl(2-mesityl-1H-inden-1-yl)phosphine; DME = 1,2-dimethoxyethane; dba = dibenzylideneacetone.
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Mechanistic investigation. Standard conditions: nitroarene or potential intermediate (0.20 mmol, 1.0 equiv. or 0.10 mmol, 0.5 equiv.), alkene (0.40 mmol, 2.0 equiv.), NiBr2(diglyme) (0.02 mmol, 10 mol%), L8 (0.03 mmol, 15 mol%), DEMS (2.0 mmol, 10.0 equiv.), Na2CO3 (0.60 mmol, 3.0 equiv.), TBAI (0.10 mmol, 0.5 equiv.), Mg powder (0.10 mmol, 0.5 equiv.), solvent (1,4-dioxane∶ MeOH = 5∶1, 1.20 mL, 0.167 mol/L), 50 °C, 12 h. Yields and regioisomeric ratios were determined by GC analysis with triphenylmethane as an internal standard. Total yield for the mixture of the linear product and branched product.
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Plausible reaction mechanism.
