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Experimental Procedure. Method A: A mixture of substrate (0.5 mmol, Pd(OAc)2 (0.025 mmol, 5 mol , and benzoyl peroxide (1 mmol; addition interval 4 × 0.5 equiv/0.5 h) in acetonitrile (1 mL) and acetic acid (1 mL) was sealed in a 8 mL vial with a Teflon-lined cap. The mixture was heated at 100 °C (oil bath temperature) for 2 h. Method B: A mixture of substrate (0.5 mmol, Pd(OAc)2 (0.025 mmol, 5 mol , and benzoyl peroxide (1 mmol) in acetonitrile (1 mL) and acetic acid (1 mL) was sealed in a 8 mL vial with a Teflon-lined cap. The mixture was heated at 160 °C (oil bath temperature) for 10 min. Method C: A mixture of substrate (0.5 mmol, Pd(OAc)2 (0.05 mmol, 10 mol , and benzoyl peroxide (1 mmol) in acetonitrile (2 mL) was sealed in a 8 mL vial with a Teflon-lined cap. The mixture was heated at 160 °C (oil bath temperature) for 10 min. Caution: Aryl acylperoxides are potentially explosive and should be handled with c
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2 (0.05 mmol, 10 mol %), and benzoyl peroxide (1 mmol) in acetonitrile (2 mL) was sealed in a 8 mL vial with a Teflon-lined cap. The mixture was heated at 160 °C (oil bath temperature) for 10 min. Caution: Aryl acylperoxides are potentially explosive and should be handled with care and in small quantities.
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68149118459
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2 catalyst, la (87%) was recovered with trace quantities of isomeric o-, m-, and p-arylated products being observed by GC-MS.
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2 catalyst, la (87%) was recovered with trace quantities of isomeric o-, m-, and p-arylated products being observed by GC-MS.
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68149086921
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Performing the arylation of oximes in MeCN/AcOH medium produced a complicated mixture, and extensive hydrolysis of the oximes was observed (see Table S10 in Supporting Information for results).
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Performing the arylation of oximes in MeCN/AcOH medium produced a complicated mixture, and extensive hydrolysis of the oximes was observed (see Table S10 in Supporting Information for results).
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See Supporting Information for details
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See Supporting Information for details.
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With 2-methoxylbenzoyl peroxide as reagent, no arylation but carboxylation products formation was observed with recovery of la
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With 2-methoxylbenzoyl peroxide as reagent, no arylation but carboxylation products formation was observed with recovery of la.
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0000139820
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A plausible alternative route to arylcarboxylation is via oxidative addition of the peroxide to Pd(II) to give a reactive Pd(IV) species, which would subsequently undergo reductive elimination; see: Canty, A. J.; Jin, H.; Skelton, B. W.; White, A. H. Inorg. Chem. 1998, 37, 3975.
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A plausible alternative route to arylcarboxylation is via oxidative addition of the peroxide to Pd(II) to give a reactive Pd(IV) species, which would subsequently undergo reductive elimination; see: Canty, A. J.; Jin, H.; Skelton, B. W.; White, A. H. Inorg. Chem. 1998, 37, 3975.
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Ritter and co-workers disclosed a radical mechanism for the Pd(OAc)2-catalyzed heteroatom C-H functionalization, and formation of a Pd(III) -Pd(III) intermediate was proposed; see: Powers, D. C.; Ritter, T. Nat. Chem. 2009, 1, 302-309.
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Ritter and co-workers disclosed a radical mechanism for the Pd(OAc)2-catalyzed heteroatom C-H functionalization, and formation of a Pd(III) -Pd(III) intermediate was proposed; see: Powers, D. C.; Ritter, T. Nat. Chem. 2009, 1, 302-309.
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