4-FLUOROBENZOIC ANHYDRIDE

General procedure: TsCl (0.5 mmol, 0.10 g) was added to the mixture of carboxylic acid (1 mmol) and KA flame-dried 4.0 mL vial was charged with Pd(TFA)2 (9.9 mg, 0.03 mmol, 10 mol%), benzoquinone (3.3mg, 0.03 mmol, 10 mol%), CuI (17.1 mg, 0.09 mmol, 30 mol%), AsPh3 (27.6 mg, 0.09 mmol, 30 mol%), 1t(59.1mg, 0.3 mmol, 1.0 equiv, based on monomer) and substituted General procedure: A flame-dried 4.0 mL vial was charged with Pd(TFA)2 (9.9 mg, 0.03 mmol, 10 mol%), benzoquinone (3.3mg, 0.03 mmol, 10 mol%), CuI (17.1 mg, 0.09 mmol, 30 mol%), AsPh3 (27.6 mg, 0.09 mmol, 30 mol%), arylboroxine (0.3 mmol, 1.0 equiv, based on monomer) and substituted benzoic anhydride (0.6 mmol, 2.0equiv). The vial was directly transferred into a nitrogen-filled glovebox without caps. Then, K2CO3 (6.2 mg, 0.045 mmol, 15 mol%) and 4A molecular sieves (400 mg) were added. In another 4.0 mL vial, NBE (16.9mg, 0.18 mmol) was dissolved in 1.5 mL dry toluene. 0.5 mL of this NBE solution (5.64 mg, 0.06 mmol, 20mol%) was transferred into the reaction mixture, before another 3.5 mL dry toluene was added. The vialwas tightly sealed, transferred out of glovebox and stirred on a pie-block preheated to 100 oC for 14 hours.After completion of the reaction, the mixture was filtered through a thin pad of silica gel. The filter cakewas washed with ethyl acetate and the combined filtrate was concentrated. The residue was loaded to asmall amount of silica gel and then purified by flash column chromatography on silica gel to give thedesired ortho acylation product.General procedure: A flame-dried 4.0 mL vial was charged with Pd(TFA)2 (9.9 mg, 0.03 mmol, 10 mol%), benzoquinone (3.3mg, 0.03 mmol, 10 mol%), CuI (17.1 mg, 0.09 mmol, 30 mol%), AsPh3 (27.6 mg, 0.09 mmol, 30 mol%), arylboroxine (0.3 mmol, 1.0 equiv, based on monomer) and substituted benzoic anhydride (0.6 mmol, 2.0equiv). The vial was directly transferred into a nitrogen-filled glovebox without caps. Then, K2CO3 (6.2 mg, 0.045 mmol, 15 mol%) and 4A molecular sieves (400 mg) were added. In another 4.0 mL vial, NBE (16.9mg, 0.18 mmol) was dissolved in 1.5 mL dry toluene. 0.5 mL of this NBE solution (5.64 mg, 0.06 mmol, 20mol%) was transferred into the reaction mixture, before another 3.5 mL dry toluene was added. The vialwas tightly sealed, transferred out of glovebox and stirred on a pie-block preheated to 100 oC for 14 hours.After completion of the reaction, the mixture was filtered through a thin pad of silica gel. The filter cakewas washed with ethyl acetate and the combined filtrate was concentrated. The residue was loaded to asmall amount of silica gel and then purified by flash column chromatography on silica gel to give thedesired ortho acylation product.General procedure: A flame-dried 4.0 mL vial was charged with Pd(TFA)2 (9.9 mg, 0.03 mmol, 10 mol%), benzoquinone (3.3mg, 0.03 mmol, 10 mol%), CuI (17.1 mg, 0.09 mmol, 30 mol%), AsPh3 (27.6 mg, 0.09 mmol, 30 mol%), arylboroxine (0.3 mmol, 1.0 equiv, based on monomer) and substituted benzoic anhydride (0.6 mmol, 2.0equiv). The vial was directly transferred into a nitrogen-filled glovebox without caps. Then, K2CO3 (6.2 mg, 0.045 mmol, 15 mol%) and 4A molecular sieves (400 mg) were added. In another 4.0 mL vial, NBE (16.9mg, 0.18 mmol) was dissolved in 1.5 mL dry toluene. 0.5 mL of this NBE solution (5.64 mg, 0.06 mmol, 20mol%) was transferred into the reaction mixture, before another 3.5 mL dry toluene was added. The vialwas tightly sealed, transferred out of glovebox and stirred on a pie-block preheated to 100 oC for 14 hours.After completion of the reaction, the mixture was filtered through a thin pad of silica gel. The filter cakewas washed with ethyl acetate and the combined filtrate was concentrated. The residue was loaded to asmall amount of silica gel and then purified by flash column chromatography on silica gel to give thedesired ortho acylation product.General procedure: A flame-dried 4.0 mL vial was charged with Pd(TFA)2 (9.9 mg, 0.03 mmol, 10 mol%), benzoquinone (3.3mg, 0.03 mmol, 10 mol%), CuI (17.1 mg, 0.09 mmol, 30 mol%), AsPh3 (27.6 mg, 0.09 mmol, 30 mol%), arylboroxine (0.3 mmol, 1.0 equiv, based on monomer) and substituted benzoic anhydride (0.6 mmol, 2.0equiv). The vial was directly transferred into a nitrogen-filled glovebox without caps. Then, K2CO3 (6.2 mg, 0.045 mmol, 15 mol%) and 4A molecular sieves (400 mg) were added. In another 4.0 mL vial, NBE (16.9mg, 0.18 mmol) was dissolved in 1.5 mL dry toluene. 0.5 mL of this NBE solution (5.64 mg, 0.06 mmol, 20mol%) was transferred into the reaction mixture, before another 3.5 mL dry toluene was added. The vialwas tightly sealed, transferred out of glovebox and stirred on a pie-block preheated to 100 oC for 14 hours.After completion of the reaction, the mixture was filtered through a thin pad of silica gel. The filter cakewas washed with ethyl acetate and the combined filtrate was concentrated. The residue was loaded to asmall amount of silica gel and then purified by flash column chromatography on silica gel to give thedesired ortho acylation product.General procedure: A flame-dried 4.0 mL vial was charged with Pd(TFA)2 (9.9 mg, 0.03 mmol, 10 mol%), benzoquinone (3.3mg, 0.03 mmol, 10 mol%), CuI (17.1 mg, 0.09 mmol, 30 mol%), AsPh3 (27.6 mg, 0.09 mmol, 30 mol%), arylboroxine (0.3 mmol, 1.0 equiv, based on monomer) and substituted benzoic anhydride (0.6 mmol, 2.0equiv). The vial was directly transferred into a nitrogen-filled glovebox without caps. Then, K2CO3 (6.2 mg, 0.045 mmol, 15 mol%) and 4A molecular sieves (400 mg) were added. In another 4.0 mL vial, NBE (16.9mg, 0.18 mmol) was dissolved in 1.5 mL dry toluene. 0.5 mL of this NBE solution (5.64 mg, 0.06 mmol, 20mol%) was transferred into the reaction mixture, before another 3.5 mL dry toluene was added. The vialwas tightly sealed, transferred out of glovebox and stirred on a pie-block preheated to 100 oC for 14 hours.After completion of the reaction, the mixture was filtered through a thin pad of silica gel. The filter cakewas washed with ethyl acetate and the combined filtrate was concentrated. The residue was loaded to asmall amount of silica gel and then purified by flash column chromatography on silica gel to give thedesired ortho acylation product.

Molecular Weight:262.21
XLogP3:3.4
Hydrogen Bond Acceptor Count:5
Rotatable Bond Count:4
Exact Mass:262.04415044
Monoisotopic Mass:262.04415044
Topological Polar Surface Area:43.4
Heavy Atom Count:19
Complexity:298
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes