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Reactions carried out at high pressures of CO might well be successful, but were not pursued in favor of perturbing the reaction outcome through other variables as described in the text
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Reactions carried out at high pressures of CO might well be successful, but were not pursued in favor of perturbing the reaction outcome through other variables as described in the text.
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33846791850
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Four-coordinate, square-planar palladium(II) complexes are coordinatively unsaturated (16-electron), but often react by further ligand loss to a three-coordinate, 14-electron intermediate.
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Four-coordinate, square-planar palladium(II) complexes are coordinatively unsaturated (16-electron), but often react by further ligand loss to a three-coordinate, 14-electron intermediate.
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Extending the reaction time from 16 to 36 h or raising the reaction temperature from 50 to 60°C did not increase the yield of the ketone. However, an effective reaction was resumed when additional CuTC and phenylboronic acid were added to the reaction mixture after 14 h, an indication that the Pd catalyst was still robust. For example, a mixture of thiol ester N,N-bis-Boc-phenylalanine p, chlorophenylthiol ester (56.4 mg, 0.11 mmol, 1.0 equiv, CuTC (32.7 mg, 0.17 mmol, 1.5 equiv, phenylboronic acid (21.4 mg, 0.18 mmol, 1.5 equiv, Pd2(dba)3 (5.6 mg, 0.061 mmol, 0.05 equiv, PPh3 (11.9 mg, 0.045 mmol, 0.4 equiv, and PMe2Ph (6.5 μL, 0.045 mmol, 0.4 equiv) in 3 mL of dry THF was stirred at 50°C for 14 h. Then, additional CuTC (21.9 mg, 0.11 mmol, 1.0 equiv, phenylboronic acid 14.1 mg, 0.11 mmol, 1.0 equiv, and 1.0 mL of dry THF were added. The reaction was stirred for another 8 h at 50°C. After the aqueous wor
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2Ph (6.5 μL, 0.045 mmol, 0.4 equiv) in 3 mL of dry THF was stirred at 50°C for 14 h. Then, additional CuTC (21.9 mg, 0.11 mmol, 1.0 equiv), phenylboronic acid (14.1 mg, 0.11 mmol, 1.0 equiv). and 1.0 mL of dry THF were added. The reaction was stirred for another 8 h at 50°C. After the aqueous workup, the yield of the ketone (81%) was determined by proton NMR using pentamethylbenzene as an internal standard.
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THF/hexanes solvent mixtures were used to maintain a low concentration of the active Cu(I) carboxylate in solution throughout the course of the cross-coupling reaction. Cu(I) carboxylate that is not complexed to the thiol ester or to the putative palladium(II) thiolate catalytic intermediate leads to competitive destruction of the boronic acid by a Cu-mediated protodeborylation.
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THF/hexanes solvent mixtures were used to maintain a low concentration of the active Cu(I) carboxylate in solution throughout the course of the cross-coupling reaction. Cu(I) carboxylate that is not complexed to the thiol ester or to the putative palladium(II) thiolate catalytic intermediate leads to competitive destruction of the boronic acid by a Cu-mediated protodeborylation.
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