(R,R)-TsDPEN

(R, R) -1, 2-diphenyl-ethylenediamine (20 mmol, available from Kling 24650) was dissolvedIn dichloromethane (30 mL)At 0 ° CWill be dissolved in dichloroethane (30mL)Of p-methylphenyl sulfonyl chloride(20 mmol, available from Kling 283322)Drip into it (30min drip finished), Continue to react at 0 ° C for 1 h, then rotary evaporator under reduced pressure, The solid was separated and purified by column chromatography (eluent dichloromethane / methanol 10: 1 by volume)Thus, 15 mmol of a chiral diamine represented by the formula (R, R) - (3-1-1-1)The yield is 75percent(1) (R, R)-1, 2-diphenyl-ethylenediamine (20 mmol, Purchased from Valinway Technology Corporation No. 24694) dissolved in dichloromethane (30 mL), And p-methylphenylsulfonyl chloride dissolved in dichloroethane (30 mL) at 0°C(20 mmol, purchased from the JV of Schering Technology, Inc. 283322) was added dropwise (completed within 30 min), and the reaction was continued at 0 °C for 1 h. The mixture was then evaporated under reduced pressure and the solid was purified by column chromatography.(The eluent was a 10:1 volume ratio of dichloromethane/methanol) to give 15 mmolThe chiral diamine represented by (R, R)-(3-1-1-1) has a yield of 75percent.(1) Dissolving (R, R)-1, 2-diphenyl-ethylenediamine (20 mmol, available from Valinway Technology Corporation No. 24694)p-Methylphenylsulfonyl chloride (20 mmol, from Schering-Plant Technology, Inc. 283322 grade) dissolved in dichloroethane (30 mL) was added dropwise to dichloromethane (30 mL) in dichloromethane (30 mL). After 30 minutes, the reaction was continued at 0°C for 1 hour, and then the mixture was evaporated under reduced pressure. The solid was purified by column chromatography (eluent: 10:1 dichloromethane/methanol) to give 15 mmol. The chiral diamine of the formula (R, R)-(3-1-1-1) has a yield of 75percent.General procedure: Catalysts 1a–1d were similarly prepared. Catalyst 1a was prepared as follows: (1R, 2R)-(+)-(1, 2)-DPEN (0.50g, 2.40mmol) and Et3N (1mL) were dispersed into 20mL anhydrous tetrahydrofuran (THF). A solution of p-TsCl (0.45g, 2.40mmol) in 5 mL anhydrousTHF was added to the aforementioned solution. The reaction mixture was stirred vigorously at 0° C for 12 h and then evaporated to generate the crude product. The crude was purified by column chromatography on silica gel (200–300 mesh, PE=EtOAc1:1).(1)(R, R) -1, 2-diphenyl-ethylenediamine (20 mmol, available from Kling 24650) was dissolvedIn dichloromethane (30 mL)At 0 CWill be dissolved in dichloroethane (30mL)Of p-methylphenyl sulfonyl chloride(20 mmol, available from Kling 283322)Drip into it (30min drip finished), Continue to react at 0 C for 1 h, then rotary evaporator under reduced pressure, The solid was separated and purified by column chromatography (eluent dichloromethane / methanol 10: 1 by volume)Thus, 15 mmol of a chiral diamine represented by the formula (R, R) - (3-1-1-1)The yield is 75%(1) (R, R)-1, 2-diphenyl-ethylenediamine (20 mmol, Purchased from Valinway Technology Corporation No. 24694) dissolved in dichloromethane (30 mL), And p-methylphenylsulfonyl chloride dissolved in dichloroethane (30 mL) at 0C(20 mmol, purchased from the JV of Schering Technology, Inc. 283322) was added dropwise (completed within 30 min), and the reaction was continued at 0 C for 1 h. The mixture was then evaporated under reduced pressure and the solid was purified by column chromatography.(The eluent was a 10:1 volume ratio of dichloromethane/methanol) to give 15 mmolThe chiral diamine represented by (R, R)-(3-1-1-1) has a yield of 75%.(1) Dissolving (R, R)-1, 2-diphenyl-ethylenediamine (20 mmol, available from Valinway Technology Corporation No. 24694)p-Methylphenylsulfonyl chloride (20 mmol, from Schering-Plant Technology, Inc. 283322 grade) dissolved in dichloroethane (30 mL) was added dropwise to dichloromethane (30 mL) in dichloromethane (30 mL). After 30 minutes, the reaction was continued at 0C for 1 hour, and then the mixture was evaporated under reduced pressure. The solid was purified by column chromatography (eluent: 10:1 dichloromethane/methanol) to give 15 mmol. The chiral diamine of the formula (R, R)-(3-1-1-1) has a yield of 75%.General procedure: Catalysts 1a-1d were similarly prepared. Catalyst 1a was prepared as follows: (1R, 2R)-(+)-(1, 2)-DPEN (0.50g, 2.40mmol) and Et3N (1mL) were dispersed into 20mL anhydrous tetrahydrofuran (THF). A solution of p-TsCl (0.45g, 2.40mmol) in 5 mL anhydrousTHF was added to the aforementioned solution. The reaction mixture was stirred vigorously at 0 C for 12 h and then evaporated to generate the crude product. The crude was purified by column chromatography on silica gel (200-300 mesh, PE=EtOAc1:1).(R)-methyl 9-bromo-4-hydroxy-1, 2, 3, 4-tetrahydrobenzo[4, 5]imidazo[1, 2-a]pyridine-7-carboxylate (46f). A solution of dichlororuthenium;1-isopropyl-4-methyl-benzene (18.00 mg, 29.40 umol), General procedure: To a 50-ml glass round-bottom flask was added sequentially the primary amine 2 (1.0 mmol; aliphatic, aromatic or heteroaromatic; as free naked amine or as HCl, MsOH, TsOH or tartrate salt), FSO2N3 solution (containing 1.0 mmol FSO2N3, approximately 200 mM in DMF/MTBE 1:1, v/v, approximately 5 ml, volume adjusted according to the concentration; prepared according to the above procedure and diluted with equal volume of DMF) and aqueous KHCO3 solution (3.0 M, 1.33 ml, containing 4.0 mmol KHCO3). The reaction mixture was stirred for 5 min at room temperature, while monitoring by LC-MS. After completion, EtOAc (40 ml) was added and the mixture was washed sequentially with brine (60 ml × 6), water (60 ml × 2) and brine (60 ml), dried over Na2SO4, concentrated by rotary evaporation and dried under vacuum to afford the azide product 3. For products containing acidic functional groups, this extraction process was modified with acidified aqueous phase (acidified with aqueous HCl). Detailed procedures and the various modifications, as well as the characterization data for each compound, can be found in Supplementary Information 1.

(R,R)-N-(2-Amino-1,2-diphenylethyl)-p-toluenesulfonamide is used as a catalyst in stereoselective preparation of aromatic ketone derivatives as well as other chiral organic compounds.

Molecular Weight:366.5
XLogP3:3.4
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:4
Rotatable Bond Count:6
Exact Mass:366.14019912
Monoisotopic Mass:366.14019912
Topological Polar Surface Area:80.6
Heavy Atom Count:26
Complexity:511
Defined Atom Stereocenter Count:2
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes