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General Procedure for the Silver Acetate Catalyzed Mannich Reactions (Table 4, entry 1, Ligand (0.0075 mmol) and AgOAc (1.2 mg, 0.007 mmol) were placed in a dried Schlenk tube under a nitrogen atmosphere and Et2O (1.0 mL) was added. The mixture was stirred at room temperature for about 0.5 h. After cooling to the indicated temperature, α,α-dicyanoolefin (0.23 mmol) was added as a solution in Et2O (1.0 mL) followed by addition of aldimine (0.276 mmol, Progress of the Ag-catalyzed Mannich reaction was typically monitored by TLC analysis. Upon consumption of the limiting reagent, the reaction was isolated by a short column of silica gel chromatography directly. The ratio (syn/anti) was determined by NMR spectroscopic analysis of the crude product. The crude adducts were purified by column chromatography on silica gel
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2O (1.0 mL) followed by addition of aldimine (0.276 mmol). Progress of the Ag-catalyzed Mannich reaction was typically monitored by TLC analysis. Upon consumption of the limiting reagent, the reaction was isolated by a short column of silica gel chromatography directly. The ratio (syn/anti) was determined by NMR spectroscopic analysis of the crude product. The crude adducts were purified by column chromatography on silica gel.
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Selected physical and spectral data for 7a: white solid, 64% ee, α]D23 -82.9 (c 1.03, CHCl3, Rf 0.55 (PE-EtOAc, 5:1, HPLC (Chiralpak AD-H column; i-PrOH-hexane, 95:5; 0.8 mL/min; 254 nm; 30°C, t R(minor, 8.2 min, tR(major, 13.6 min; 1H NMR (400 MHz, CDCl3, δ, 8.06 (d, J, 7.9 Hz, 1 H, 7.51 (t, J, 7.4 Hz, 1 H, 7.41-7.24 (m, 7 H, 4.94-4.92 (m, 1 H, 4.53 (t, J, 10.4 Hz, 1 H, 3.72-3.68 (m, 1 H, 2.89-2.85 (m, 1 H, 2.70-2.66 (m, 1 H, 1.93-1.89 (m, 1 H, 1.51-1.47 (m, 1 H, 1.42 (s, 9 H, 13C NMR 100 MHz, CDCl3, δ, 175.1, 154.7, 140.0, 138.9, 133.5, 129.8, 129.4, 128.7, 128.6, 127.0, 126.9, 114.2, 113.6, 82.1, 80.2, 57.5, 49.1, 28.3, 25.9, 25.2
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3): δ = 175.1, 154.7, 140.0, 138.9, 133.5, 129.8, 129.4, 128.7, 128.6, 127.0, 126.9, 114.2, 113.6, 82.1, 80.2, 57.5, 49.1, 28.3, 25.9, 25.2.
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