* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
In diethyl ether; at 20℃;Inert atmosphere; Molecular sieve;
General procedure: To a Et2O solution of anorganoboronic acid (1.00 equiv) and 2,2-dimethylpropane-1,3-diol (neopentyl glycol)(1.02 equiv), 4A molecular sieves was added and the reaction mixture was stirred atroom temperature. After the reaction finished, the reaction mixture was filtered andconcentrated in vacuo. The residue was subjected to flash column chromatography(eluent: petroleum ether/ethyl acetate) or recrystallization to obtain the desired product
Example 9: Borylation with tetrakis - borylation of aryl bromides (Table 7)KOAc (1.84 g, 18.6 mmol, 3.0 eq.), neopentyl glycol (1.56 g, 15.0 mmol, 2.4 eq.) and tetrakis (1 .48 g, 7.50 mmol, 1 .2 eq.) were suspended in toluene (25 ml) and heated to 80C for 30 min. Afterwards a solution of the corresponding aryl bromide (see Table 7) and Pd-catalyst[Pd(PPh3)4 (144 mg, 0.125 mmol, 2 mol-%) or PdC (dppf) (102 mg, 0.125 mmol, 2 mol-%)] in toluene (5 ml) was added at 80C. The conversion of the reaction was followed by GC. The final product was identified by its mass using GC-MS-technology. Table 7: Examples of the borylation with tetrakis/neopentyl glycolTable 8: Retention times of aryl bromides and their borylation products
With 3,3-dimethyl-butan-2-one; carbonyl bis(hydrido)tris(triphenylphosphine)ruthenium(II); at 150℃; for 4h;Microwave irradiation; Inert atmosphere;
General procedure: A dried Biotage microwave vial equipped with a magnetic stirring bar and anitrogen inlet was sequentially charged with fluorenone (1) (0.5 mmol), boronic ester (6) (0.5 - 1mmol), pinacolone (0.5 mL) and RuH2(CO)(PPh3)3 (10 mol%). The reaction mixture was heatedunder MW irradiation at 150 C for 2.5 - 8 h. The reaction mixture was extracted with EtOAc (15mL), washed with brine, subjected to filtration, dried (Na2SO4) and concentrated under reducedpressure. Purification using flash column chromatography on silica gel (eluting with 1:9hexanes/ethyl acetate) afforded product (2).
4-((1S*,2R*,3S*)-3-(3-methoxyphenyl)-2-methyl-2-phenylcyclopropyl)morpholine[ No CAS ]
4-(3-(3-methoxyphenyl)-2-methyl-2-phenylcyclopropyl)morpholine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
Add tetrahydrofuran as a solvent (2 ml) in a 25 ml reaction tube, and sequentially add cuprous chloride (0.010 mmol),Dppbz L1 (5.4 mg, 0.06 mmol),Stir at room temperature for 2 min; add m-CPBA (2 mg, 0.01 mmol),Sodium tert-butoxide (28.8 mg, 0.3 mmol) was stirred for 2 min;Then a molar amount of substrate 1.2 molar amount of 3-methoxyphenylboronic acid neopentyl glycol ester (50.3 mg, 0.24 mmol),Stir for about 2 min; add 3-methyl-3-phenylcyclopropene (0.2 mmol),4-(N,N-diethyl)benzoyloxymorpholine(93 mg, 0.24 mmol) of the reaction system was stirred at room temperature.TLC point plate monitoring, after the reaction is complete,Separated and purified by column chromatography,An oily liquid was obtained which was subjected to 1H NMR (as shown in Figure 19), 13C.NMR (shown in Figure 20), the structure was determined to be Formula 10, the weighing weight was 43.7 mg, the calculated yield was 66%, and dr = 94:6;
With N,N,N,N,-tetramethylethylenediamine; copper(l) chloride; lithium tert-butoxide; In N,N-dimethyl-formamide; at 60℃; for 10h;Sealed tube; Inert atmosphere;
(1) Cuprous chloride (CuCl, 10 mol%), tetramethylethylenediamine (TMEDA, 15 mol%), tert-butanol under airLithium (LiOtBu, 2.5 eq), m-methoxy-aryl neopentyl glycol boron ester (2 eq) was added to a tube with a magnetic tubeIn the sealed reaction tube, the reaction tube was flushed with argon three times. Under the protection of argon, 0.6 mL of N,N-dimethylformyl was added to the reaction tube.Amine, then add vinyl epoxy (0.25 mmol) to the reaction solution under argon, plug the piston, and place in a 60 C oil bathThe reaction was stirred for 10 hours.(2) The material obtained in the step (1) is quenched by adding saturated ammonium chloride, and fully mixed with ethyl acetate, using short silicon.After the column has filtered off the solid residue, the organic phase is retained.(3) spinning the solvent in the organic phase obtained in the step (2) to obtain a crude product, which is then purified by a silica gel column.Things. The eluent was a mixture of petroleum ether and ethyl acetate with an isolated yield of 86% and a product purity of 100%.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Sealed tube;
Gold catalyst 1a (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.02 mmol), PhI (OAc) 2 (84 mg, 0.26 mmol) and C2H3Cl3 (provided by Shanghai Lingfeng Chemical Reagent Co., Ltd.) were added to the sealed tube. Same as .) (1 ml) and vigorously stirred at room temperature for 30 min. Subsequently, a mixed solution of (55.2 mg, 0.2 mmol) and (57.2 mg, 0.26 mmol) of C2H3Cl3 (1 ml) was dropped into a sealed tube and reacted at 110 C for 2 h. The reaction solution was concentrated, dried, and subjected to column chromatography to give the product 44.3 mg ( petroleum ether), yield 70%.
70%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;Catalytic behavior;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 1h;Sealed tube;
Gold catalyst 1a (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.02 mmol), PhI(OAc) 2 (84 mg, 0.26 mmol) and C2H3Cl3 (1 ml) were added to the dried tube and stirred vigorously at room temperature. 30min. Subsequently, a mixed solution of (45.8 mg, 0.2 mmol) and (57.2 mg, 0.26 mmol) of C2H3Cl3 (1 ml) was dropped into a sealed tube and reacted at 110 C for 1 h. The reaction solution was concentrated, dried, and purified by column chromatography to give the product 38.4 mg ( petroleum ether: ethyl acetate = 100:1), yield 73%.
73%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 1h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
3'-methoxy-[1,1'-biphenyl]-4-yl trifluoromethanesulfonate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
61%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 1h;Sealed tube;
Gold catalyst 1a (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.02 mmol), PhI(OAc) 2 (84 mg, 0.26 mmol) and C2H3Cl3 (1 ml) were added to the dried tube and stirred vigorously at room temperature. 30min. Subsequently, a mixed solution of (59.7 mg, 0.2 mmol) and (57.2 mg, 0.26 mmol) of C2H3Cl3 (1 ml) was dropped into a sealed tube, and reacted at 110 C for 1 h. The reaction solution was concentrated, dried, and subjected to column chromatography to give the product 40.5 mg ( petroleum ether: ethyl acetate = 100:1), yield 61%.
61%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 1h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 1h;Sealed tube;
Gold catalyst 1a (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.02 mmol), PhI(OAc) 2 (84 mg, 0.26 mmol) and C2H3Cl3 (1 ml) were added to the dried tube and stirred vigorously at room temperature. 30min. Subsequently, a mixed solution of (35.7 mg, 0.2 mmol) and (57.2 mg, 0.26 mmol) of C2H3Cl3 (1 ml) was dropped into a sealed tube and reacted at 110 C for 1 h. The reaction solution was concentrated, dried, and purified by column chromatography to give the product 24.2mg ( petroleum ether: ethyl acetate = 100:1), yield 57%.
57%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 1h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
3′-methoxy-[1,1′-biphenyl]-4-carbonitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
52%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Sealed tube;
Gold catalyst 1a (12.5 mg, 0.014 mmol), AgOTs (16.7 mg, 0.06 mmol), PhI(OAc) 2 (84 mg, 0.26 mmol) and C2H3Cl3 (1 ml) were added to the dried tube and stirred vigorously at room temperature. 30min. Subsequently, a mixed solution of (35.1 mg, 0.2 mmol) and (57.2 mg, 0.26 mmol) of C2H3Cl3 (1 ml) was dropped into a sealed tube and reacted at 110 C for 2 h. The reaction solution was concentrated, dried, and subjected to column chromatography to give the product 21.8 mg ( petroleum ether: ethyl acetate=40:1-30:1), yield 52%.
52%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Sealed tube;
Gold catalyst 1a (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.02 mmol), PhI(OAc) 2 (84 mg, 0.26 mmol) and C2H3Cl3 (1 ml) were added to the dried tube and stirred vigorously at room temperature. 30min. Subsequently, a mixed solution of (41.7 mg, 0.2 mmol) and (57.2 mg, 0.26 mmol) of C2H3Cl3 (1 ml) was dropped into a sealed tube, and reacted at 110 C for 2 h. The reaction solution is concentrated, dry-loaded, and column chromatographyTo the product 33.9 mg (petroleum ether: ethyl acetate = 30:1), yield 70%.
70%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
triisopropyl((3'-methoxy-[1,1'-biphenyl]-4-yl)oxy)silane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
62%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Sealed tube;
Gold catalyst 1a (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.02 mmol), PhI(OAc) 2 (84 mg, 0.26 mmol) and C2H3Cl3 (1 ml) were added to the dry sealed tube, and vigorously stirred at room temperature. 30min. Subsequently (41.7 mg, 0.2 mmol) and (TIPS is an i-Pr3Si group)A mixed solution of (57.2 mg, 0.26 mmol) of C2H3Cl3 (1 ml) was dropped into a sealed tube and reacted at 110 C for 2 h. Reaction solutionReduction, dry loading, column chromatography gave the product 44.2 mg (petroleum ether: ethyl acetate = 100:1), the yield was 62%.
62%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 1h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Sealed tube;
Gold catalyst 1a (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.02 mmol), PhI(OAc) 2 (84 mg, 0.26 mmol) and C2H3Cl3 (1 ml) were added to the dried tube and stirred vigorously at room temperature. 30min. Subsequently, a mixed solution of (38.9 mg, 0.2 mmol) and (57.2 mg, 0.26 mmol) of C2H3Cl3 (1 ml) was dropped into a sealed tube, and reacted at 110 C for 2 h. The reaction solution was concentrated, dried, and subjected to column chromatography to give the product 22.8mg ( petroleum ether: ethyl acetate = 5:1), yield 50%.
50%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
3-methoxy-4'-(phenylethynyl)-1,1'-biphenyl[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
47%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Sealed tube;
Gold catalyst 1a (12.5 mg, 0.014 mmol), AgOTs (16.7 mg, 0.06 mmol), PhI(OAc) 2 (129 mg, 0.4 mmol) and DCM (1 ml) were added to the dried tube and stirred vigorously at room temperature. 30min. Subsequently, a mixed solution of (50.1 mg, 0.2 mmol) and (57.2 mg, 0.26 mmol) of DCM (1 ml) was dropped into a sealed tube and reacted at 110 C for 2 h. The reaction solution was concentrated, dried, and purified by column chromatography to give the product 26.7mg ( petroleum ether: ethyl acetate = 100:1), yield 47%.
42%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In dichloromethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
3-(trimethylsilyl)phenyl methanesulfonate[ No CAS ]
3'-methoxy-[1,1'-biphenyl]-3-yl methanesulfonate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
64%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Sealed tube;
Gold catalyst 1a (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.02 mmol), PhI(OAc) 2 (84 mg, 0.26 mmol) and C2H3Cl3 (1 ml) were added to the dried tube and stirred vigorously at room temperature. 30min. Subsequently, a mixed solution of (48.9 mg, 0.2 mmol) and (57.2 mg, 0.26 mmol) of C2H3Cl3 (1 ml) was dropped into a sealed tube and reacted at 110 C for 2 h. The reaction solution was concentrated, dried, and subjected to column chromatography to give the product 35.6 mg ( petroleum ether: ethyl acetate = 7:1) 64%.
64%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 1h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With (triphenylphosphine)gold(I) chloride; silver(I) 4-methylbenzenesulfonate; In 1,1,1-trichloroethane; at 110℃; for 1h;Inert atmosphere; Schlenk technique;
In order to investigate the transmetallation capability of arylboroniate3a, we carried out the above experiments. To a dried Schlenk tube was added Ph3PAuCl(9.8 mg, 0.020 mmol), AgOTs (6.7 mg, 0.024 mmol), anhydrous TCE (0.5 mL) (orPhI(OAc)2 (8.4 mg, 0.026 mmol) or nBu4NOAc (15.7 mg, 0.052 mmol) at roomtemperature under an argon atmosphere. After vigorously stirring for 30 min at roomtemperature, 3a (4.4 mg, 0.020 mmol) in 0.5 mL anhydrous TCE was added under anargon atmosphere and then the reaction mixture was stirred at 110 oC for 1 h. Thereaction mixture was was monitored by GC-MS. It was found that arylboroniate 3aonly be activated by can be activated by either Au(III)-complex or Au(I)-complex withthe external base, nBu4NOAc.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 1h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 1h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
trimethyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane[ No CAS ]
2-(3'-methoxy-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
3-methoxy-5'-phenyl-1,1':3',1''-terphenyl[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
55%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With tetrabutyl ammonium fluoride; palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; In 1-methyl-pyrrolidin-2-one; at 50℃; for 2h;Inert atmosphere;
To a 20 mL sealed tube were added 2a (55.2 mg, 0.20 mmol), 3a (57.2 mg, 0.26 mmol),BQ (54.1 mg, 0.50 mmol), rac-BINAP (3.7 mg, 0.006 mmol), TBAF (209.2 mg, 0.8mmol), and NMP (1.5 mL) sequentially. The tube was sealed and stirred at 50 C for 2h, it was cooled to room temperature. The reaction mixture was diluted with 5 mLEtOAc, washed with saturated brine, and then dried over anhydrous Na2SO4, filtered,and concentrated in vacuo. The crude product was purified by silica gelchromatography using petroleum ether as eluent to give 7a, 41.5 mg, 81%colorlessoil.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In chloroform; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver trifluoromethanesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;Catalytic behavior;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) acetate; In 1,1,2-trichloroethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;Catalytic behavior;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
4-bromo-3'-methoxy-2,5-dimethyl-1,1'-biphenyl[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
67%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In 1,1,2-trichloroethane; at 110℃; for 1h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
3'-methoxy-[1,1'-biphenyl]-2-yl trifluoromethanesulfonate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
82%
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In dichloromethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
With dichloro(N-(diphenylphosphino)-N-isopropyl-1,1-diphenylphosphinamine) digold(I); [bis(acetoxy)iodo]benzene; silver(I) 4-methylbenzenesulfonate; In dichloromethane; at 110℃; for 2h;Schlenk technique; Inert atmosphere;
General procedure: To a dried Schlenk tube was added 1f (8.9 mg, 0.01 mmol), AgOTs (11.2 mg, 0.04mmol), PhI(OAc)2 (84.0 mg, 0.26 mmol) and anhydrous TCE (1,1,2-trichloroethane, 1mL) at room temperature under an argon atmosphere. After vigorously stirring for 30min at room temperature, 2 (0.20 mmol) and 3 (0.26 mmol) in 1 mL anhydrous TCEwas added under an argon atmosphere, and then the reaction mixture was stirred at 110oC for 1-2 h. The reaction mixture was concentrated under reduced pressure and theresulting residue was purified by flash chromatography on silica gel (petroleumether/ethyl acetate) to give desired coupling product 4.
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