Cross-coupling reaction catalysts, and methods of making and using same
A technology of procatalyst and solvate, applied in the field of cross-coupling reaction catalyst and its manufacture and use, can solve the problems of economic infeasibility, high cost and the like
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Embodiment 1
[0191] Example 1: Synthesis and Characterization
[0192] Synthetic steps of the complex:
[0193] (η 3 -indenyl) 2 (μ-Cl) 2 PD 2 (3a):
[0194] PdCl 2 (1.00 g, 5.64 mmol) and NaCl (0.658 g, 11.3 mmol) were added to a 250 mL round bottom flask. Methanol (70 mL) was added and the reaction mixture was heated at 50 °C for 30 minutes, at which point it became homogeneous. The solution was allowed to cool to room temperature. Indene (0.650 g, 5.64 mmol) was added followed by Na 2 CO 3 (0.888g, 8.46mmol) and the reaction was stirred at room temperature for 2 hours. The reaction mixture was filtered and the resulting brown solid was washed with water and diethyl ether. The product was dried under vacuum to yield 3a as a brown solid. Yield: 1.22g, 84%. 1 H NMR data were consistent with those published in the literature (Sui-Seng, et al., 2004, organomet. 23:1236).
[0195] (η 3 -indenyl) 2 (μ-OTf) 2 PD 2 (3a-OTf):
[0196] Will [(η 3 -indenyl)Pd(μ-Cl)] 2 (0.10 g, ...
Embodiment 2
[0224] Example 2: Activation of the procatalyst and isolation of the L-Pd(0) intermediate
[0225]
[0226] In a 1 dram vial equipped with a micro stirring bar, add (η 3 -indenyl)Pd(L)(OTf)(0.0088mmol), K 2 CO 3 (12.2mg, 0.088mmol) and 4-(n-butyl)phenyl bromide (15.5μL, 0.088mmol) together with toluene-d 8 (0.5mL) and methanol-d 4 (0.5 mL). The mixture was stirred at room temperature for 15 minutes at which time it was filtered and the solvent was removed under reduced pressure. Dissolve the resulting solid in toluene-d 8 in and get 31 P spectrum. In each case, the only phosphorus-containing species observed was that of the oxidative addition product, (L)Pd(4-n-butylphenyl)(Br), which is consistent with literature (Lee, et al., 2014 , Inorg.Chim.Acta.422:188-192) the spectral values presented in agreement.
Embodiment 3
[0227] Example 3: (η in the Suzuki-Miyaura reaction 3 Catalytic Activity of -Indenyl)Pd(XPhos)(OTf)
[0228]
[0229]In a dinitrogen-filled glove box, mix 2-chloro-4,6-dimethoxypyrimidine (175 μL, 1.0 mmol), benzofuran-2-boronic acid (243 mg, 1.5 mmol), K 2 CO 3 (276mg, 2.0mmol) and (η 3 -Indenyl)Pd(XPhos)(OTf) (8.4 mg, 0.01 mmol) was added to a 4 dram vial equipped with a magnetic stir bar. Methanol (4 mL) and tetrahydrofuran (2 mL) were added to the vial, which was then sealed and stirred outside the glove box at 40 °C for one hour. At this point, the vial was opened to air and diethyl ether (10 mL) and H 2 O (10 mL) was added to the reaction mixture. The aqueous phase was extracted with diethyl ether (3 x 10 mL). Pass the combined organic phases through MgSO 4 Dry and filter. The supernatant was then passed through a pad of silica gel followed by removal of the solvent under reduced pressure to give the organic product. Yield: 249 mg, 97%.
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