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[ CAS No. 5994-87-6 ] {[proInfo.proName]}

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Chemical Structure| 5994-87-6
Chemical Structure| 5994-87-6
Structure of 5994-87-6 * Storage: {[proInfo.prStorage]}
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Product Details of [ 5994-87-6 ]

CAS No. :5994-87-6 MDL No. :MFCD00014766
Formula : C12H12NOP Boiling Point : -
Linear Structure Formula :- InChI Key :RIGIWEGXTTUCIQ-UHFFFAOYSA-N
M.W : 217.20 Pubchem ID :853560
Synonyms :

Calculated chemistry of [ 5994-87-6 ]

Physicochemical Properties

Num. heavy atoms : 15
Num. arom. heavy atoms : 12
Fraction Csp3 : 0.0
Num. rotatable bonds : 2
Num. H-bond acceptors : 2.0
Num. H-bond donors : 1.0
Molar Refractivity : 63.52
TPSA : 52.9 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -7.25 cm/s

Lipophilicity

Log Po/w (iLOGP) : 1.91
Log Po/w (XLOGP3) : 0.53
Log Po/w (WLOGP) : 1.87
Log Po/w (MLOGP) : 2.61
Log Po/w (SILICOS-IT) : 1.81
Consensus Log Po/w : 1.75

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 0.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -1.98
Solubility : 2.27 mg/ml ; 0.0105 mol/l
Class : Very soluble
Log S (Ali) : -1.21
Solubility : 13.3 mg/ml ; 0.0614 mol/l
Class : Very soluble
Log S (SILICOS-IT) : -4.58
Solubility : 0.00571 mg/ml ; 0.0000263 mol/l
Class : Moderately soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 4.07

Safety of [ 5994-87-6 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P280-P305+P351+P338 UN#:N/A
Hazard Statements:H302 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 5994-87-6 ]

* 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.

  • Downstream synthetic route of [ 5994-87-6 ]

[ 5994-87-6 ] Synthesis Path-Downstream   1~84

  • 1
  • [ 1499-21-4 ]
  • [ 5994-87-6 ]
YieldReaction ConditionsOperation in experiment
96% With ammonia In dichloromethane at -78 - 20℃; Diphenylphosphinic amide A solution of diphenylphosphinic chloride (7.8 g, 33 mmol) in CH2Cl2 (100 mL) in a flame-dried three-neck round-bottom flash fitted with a septum, a low-temperature condenser and a low-temperature thermometer was cooled to -78°C with a dry ice/acetone bath. Liquid ammonia was added dropwise to the solution and it was monitored by the number of drops of condensed liquid ammonia dropping into the flask. After each drop, a rise in internal temperature was observed. The solution was allowed to cool back to -78°C before addition of the next portion of ammonia, for a total of 1 mL of liquid ammonia condensed per gram of diphenylphosphinic chloride. The reaction mixture was allowed to warm to room temperature overnight and filtered. The residue was washed twice with CH2Cl2 (50 mL), and the combined filtrates were evaporated to dryness under reduced pressure to obtain the corresponding product (6.9 g, 96%) as a colourless solid: m.p. 160-162 °C; 1H NMR (CDCl3, 270 MHz) δ: 7.92-7.82 (m, 4H, Ar), 7.41-7.45 (m, 6H, Ar), 3.28 (s, 2H, NH2); 31P NMR (CDCl3, 162 MHz) δ: 22.3.
80% With ammonia In methanol; dichloromethane
76% With ammonia In tetrahydrofuran; water Inert atmosphere;
44% With hydroxylamine; sodium hydrogencarbonate In dichloromethane at -30℃; for 4h;
With ammonia; water
With ammonium hydroxide
With ammonia In dichloromethane Ambient temperature;
Multi-step reaction with 2 steps 1: 90 percent / sodium azide / acetonitrile / 16 h / Ambient temperature 2: 1.) Me2SO / 1.) 7.3 h, RT, irradiation 2.) CH2Cl2
Multi-step reaction with 2 steps 1: 90 percent / sodium azide / acetonitrile / 16 h / Ambient temperature 2: 18 percent / methanol / 6 h / 7 °C / Irradiation
Multi-step reaction with 2 steps 1: triethylamine; dmap / dichloromethane / 0.5 h / 20 °C / Inert atmosphere 2: lithium amide; ammonia / 3 h / -70 °C / Inert atmosphere
Multi-step reaction with 2 steps 1: triethylamine; dmap / dichloromethane / 20 °C / Inert atmosphere 2: lithium amide; ammonia / 0.5 h / -70 °C / Inert atmosphere
Multi-step reaction with 2 steps 1: Inert atmosphere 2: lithium amide; ammonia / -70 °C / Inert atmosphere

Reference: [1]Wahl, Benoit; Cabré, Albert; Woodward, Simon; Lewis, William [Tetrahedron Letters, 2014, vol. 55, # 42, p. 5829 - 5831]
[2]Jennings, W. Brian; Lovely, Carl J. [Tetrahedron, 1991, vol. 47, # 29, p. 5561 - 5568]
[3]Location in patent: experimental part Crampton, Rosemary H.; Hajjaji, Samir El; Fox, Martin E.; Woodward, Simon [Tetrahedron Asymmetry, 2009, vol. 20, # 21, p. 2497 - 2503]
[4]Klötzer; Stadlwieser; Raneburger [Organic Syntheses, 1986, vol. 64, p. 96 - 96]
[5]Shmurowa et al. [Zhurnal Obshchei Khimii, 1959, vol. 29, p. 2083,2087; engl. Ausg. S. 2052, 2055]
[6]Zwierzak,A.; Slusarska,E. [Synthesis, 1979, p. 691 - 693]
[7]Harger, Martin J. P. [Journal of the Chemical Society. Perkin transactions II, 1980, p. 154 - 160]
[8]Harger, Martin J.P.; Westlake, Sally [Tetrahedron, 1982, vol. 38, # 10, p. 1511 - 1516]
[9]Harger, Martin J.P.; Westlake, Sally [Tetrahedron, 1982, vol. 38, # 10, p. 1511 - 1516]
[10]Han, Zhengxu S.; Zhang, Li; Xu, Yibo; Sieber, Joshua D.; Marsini, Maurice A.; Li, Zhibin; Reeves, Jonathan T.; Fandrick, Keith R.; Patel, Nitinchandra D.; Desrosiers, Jean-Nicolas; Qu, Bo; Chen, Anji; Rudzinski, Diandra M.; Samankumara, Lalith P.; Ma, Shengli; Grinberg, Nelu; Roschangar, Frank; Yee, Nathan K.; Wang, Guijun; Song, Jinhua J.; Senanayake, Chris H. [Angewandte Chemie - International Edition, 2015, vol. 54, # 18, p. 5474 - 5477][Angew. Chem., 2015, vol. 127, # 18, p. 5564 - 5567,4]
[11]Han, Zhengxu S.; Zhang, Li; Xu, Yibo; Sieber, Joshua D.; Marsini, Maurice A.; Li, Zhibin; Reeves, Jonathan T.; Fandrick, Keith R.; Patel, Nitinchandra D.; Desrosiers, Jean-Nicolas; Qu, Bo; Chen, Anji; Rudzinski, Diandra M.; Samankumara, Lalith P.; Ma, Shengli; Grinberg, Nelu; Roschangar, Frank; Yee, Nathan K.; Wang, Guijun; Song, Jinhua J.; Senanayake, Chris H. [Angewandte Chemie - International Edition, 2015, vol. 54, # 18, p. 5474 - 5477][Angew. Chem., 2015, vol. 127, # 18, p. 5564 - 5567,4]
[12]Han, Zhengxu S.; Zhang, Li; Xu, Yibo; Sieber, Joshua D.; Marsini, Maurice A.; Li, Zhibin; Reeves, Jonathan T.; Fandrick, Keith R.; Patel, Nitinchandra D.; Desrosiers, Jean-Nicolas; Qu, Bo; Chen, Anji; Rudzinski, Diandra M.; Samankumara, Lalith P.; Ma, Shengli; Grinberg, Nelu; Roschangar, Frank; Yee, Nathan K.; Wang, Guijun; Song, Jinhua J.; Senanayake, Chris H. [Angewandte Chemie - International Edition, 2015, vol. 54, # 18, p. 5474 - 5477][Angew. Chem., 2015, vol. 127, # 18, p. 5564 - 5567,4]
  • 2
  • [ 5994-87-6 ]
  • [ 1110-78-7 ]
YieldReaction ConditionsOperation in experiment
77% With triethylamine; triphenylphosphine In tetrachloromethane; dichloromethane at 45℃; for 5h; Hexaphenylcyclotriphosphazene (CP) Diphenylphosphinamide (2.0 g, 9.2 mmol) and triphenylphosphine (2.9 g, 11.1 mmol) were dissolved in dry dichloromethane (30 mL), carbon tetrachloride (1.3 mL, 9.2 mmol) and triethylamine (1.3 mL, 9.2 mmol), and then the reaction mixture was refluxed at 45 C for 5 h. After reaction, the mixture was filtered. The solution was washed with brine, dried. After the solvent was removed, the product was recrystallized and dried under vacuum. Yield: (1.4 g, 77%). 1H NMR (Figure S2(a), 300.53 MHz, CDCl3, δ): 7.70 (m, 18H), 7.23 (d, 12 H). 13C NMR (Figure S2(b), 75.57 MHz, CDCl3, δ): 127.93, 130.33, 130.76, 139.04.31P NMR (Figure S2(c), CD2Cl2, δ): 15.02 (s).
65% With tetrachloromethane; triethylamine; triphenylphosphine In dichloromethane for 5h; Reflux; I2.5 Hexaphenylcyclotriphosphazene (1a) A suspension composed of diphenylphosphinamide (2.0 g, 9.22 mmol), triphenylphosphine (2.9 g, 11.1 mmol), carbon tetrachloride (0.89 mL, 9.22 mmol) and triethylamine (1.3 mL, 9.22 mmol) in dry dichloromethane (25 mL) is boiled under reflux for five hours. The solvent is removed on a rotary evaporator. After column chromatography with hexane:THF (1:1) as the eluent, 1.2 g (65%) of hexaphenylcyclotriphosphazene are obtained as a white substance. Further purification is effected by means of sublimation.
65% With tetrachloromethane; triethylamine; triphenylphosphine In dichloromethane for 5h; Reflux;
With tetrachloromethane; triethylamine; triphenylphosphine

  • 3
  • [ 64-17-5 ]
  • [ 5994-87-6 ]
  • [ 63528-17-6 ]
YieldReaction ConditionsOperation in experiment
80% With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide In toluene at 110℃; for 16h; Inert atmosphere; Sealed tube; Glovebox; 4.1. General Procedures General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.
65% With sodium hydroxide; potassium carbonate; methanesulfonyl chloride In benzene for 1h; Heating;
  • 4
  • [ 5994-87-6 ]
  • [ 104-88-1 ]
  • N-(4-chlorobenzylidene)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
69% With titanium(IV) tetraethanolate In tetrahydrofuran Reflux; General procedure A for the preparation of diphenylphosphinoyl benzaldimines 1a-j: General procedure: In a flame-dried two-neck round-bottom flask, diphenylphosphinic amide (0.66 g, 3.0 mmol) was added to a stirred solution of aldehyde (3.3 mmol) and Ti(OEt)4 (1.28 mL, 6.0 mmol) in THF (8.5 mL). The solution was stirred under reflux for 1-3 h depending on the substrate. The reaction was monitored by TLC until completion, the solution allowed to cool down to room temperature and the solvent evaporated. The mixture was dissolved in dichloromethane and then filtered through a pad of celite and rinsed with dichloromethane. The organic extract is concentrated to a cream solid and purified by flash chromatography column. The crude product (which is not fully soluble in the initial chromatographic eluent) was transferred as a suspension to the top of a 4 cm diameter x 9 cm high silica column using 6:4 EtOAc:Pentane. Elution with the same solvent system gave residual aldehyde. Continued elution with EtOAc afforded the product as a white solid. Yields obtained were within the range of 40-70%. Lower yields were associated with slower elution of the products and occasionally batches of over activated silica.
43% With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;
35% With titanium tetrachloride; triethylamine In dichloromethane at 0℃; for 0.416667h;
With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;
With titanium tetrachloride Inert atmosphere;
With pyrrolidine In dichloromethane for 16h; Molecular sieve; Reflux;
With pyrrolidine In dichloromethane at 65℃; for 24h; Molecular sieve;

  • 5
  • [ 5994-87-6 ]
  • [ 100-52-7 ]
  • [ 98837-46-8 ]
YieldReaction ConditionsOperation in experiment
85% With titanium tetrachloride; triethylamine In dichloromethane at 20℃; for 2h;
83% With titanium(IV) tetraethanolate In tetrahydrofuran Reflux; General procedure A for the preparation of diphenylphosphinoyl benzaldimines 1a-j: General procedure: In a flame-dried two-neck round-bottom flask, diphenylphosphinic amide (0.66 g, 3.0 mmol) was added to a stirred solution of aldehyde (3.3 mmol) and Ti(OEt)4 (1.28 mL, 6.0 mmol) in THF (8.5 mL). The solution was stirred under reflux for 1-3 h depending on the substrate. The reaction was monitored by TLC until completion, the solution allowed to cool down to room temperature and the solvent evaporated. The mixture was dissolved in dichloromethane and then filtered through a pad of celite and rinsed with dichloromethane. The organic extract is concentrated to a cream solid and purified by flash chromatography column. The crude product (which is not fully soluble in the initial chromatographic eluent) was transferred as a suspension to the top of a 4 cm diameter x 9 cm high silica column using 6:4 EtOAc:Pentane. Elution with the same solvent system gave residual aldehyde. Continued elution with EtOAc afforded the product as a white solid. Yields obtained were within the range of 40-70%. Lower yields were associated with slower elution of the products and occasionally batches of over activated silica.N-Benzylidene-P,P-diphenylphosphinicamide (1a)[3]Preparedaccording to general procedure A from benzaldehyde (3.34 mmol scale) yieldingtitle compound as a colourless solid (0.77 g, 83%): m.p. 136-137 °C; Lit.[4] 134-141 °C;1H NMR (CDCl3,270 MHz) δH 9.33 (d, 1H, JPH= 32.0 Hz, HC=N), 8.10-7.90 (m, 6H, Ar),7.66-7.45 (m, 9H, Ar); 13C NMR (CDCl3,100 MHz) δC 174.1, 136.1, 134.0, 133.2, 132.1, 131.9, 130.5, 129.3,128.8; 31P NMR (CDCl3,162 MHz) δP 25.7.
81% With toluene-4-sulfonic acid
64% With titanium tetrachloride; triethylamine In dichloromethane at 0℃; for 0.416667h;
60% With titanium tetrachloride; triethylamine In dichloromethane for 0.5h; cooling;
44% With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; for 3h; Inert atmosphere; optical yield given as %de;
With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; for 2h;
With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; for 1h;
With pyrrolidine at 60℃; for 24h; Molecular sieve;

  • 6
  • [ 5994-87-6 ]
  • [ 66-99-9 ]
  • N-(naphthalen-2-ylmethylene)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
74% With titanium(IV) tetraethanolate In tetrahydrofuran Reflux; General procedure A for the preparation of diphenylphosphinoyl benzaldimines 1a-j: General procedure: In a flame-dried two-neck round-bottom flask, diphenylphosphinic amide (0.66 g, 3.0 mmol) was added to a stirred solution of aldehyde (3.3 mmol) and Ti(OEt)4 (1.28 mL, 6.0 mmol) in THF (8.5 mL). The solution was stirred under reflux for 1-3 h depending on the substrate. The reaction was monitored by TLC until completion, the solution allowed to cool down to room temperature and the solvent evaporated. The mixture was dissolved in dichloromethane and then filtered through a pad of celite and rinsed with dichloromethane. The organic extract is concentrated to a cream solid and purified by flash chromatography column. The crude product (which is not fully soluble in the initial chromatographic eluent) was transferred as a suspension to the top of a 4 cm diameter x 9 cm high silica column using 6:4 EtOAc:Pentane. Elution with the same solvent system gave residual aldehyde. Continued elution with EtOAc afforded the product as a white solid. Yields obtained were within the range of 40-70%. Lower yields were associated with slower elution of the products and occasionally batches of over activated silica.
52% With titanium tetrachloride; triethylamine In dichloromethane at 0℃; for 0.416667h;
With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;
With titanium tetrachloride Inert atmosphere;
With pyrrolidine In dichloromethane for 16h; Molecular sieve; Reflux;
With pyrrolidine In dichloromethane at 65℃; for 24h; Molecular sieve;
With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;

  • 7
  • [ 5994-87-6 ]
  • [ 100-51-6 ]
  • [ 27127-08-8 ]
YieldReaction ConditionsOperation in experiment
99% With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide In toluene at 110℃; for 16h; Inert atmosphere; Sealed tube; Glovebox; 4.1. General Procedures General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.
95% With potassium hydroxide In toluene at 110℃; for 4h;
71% With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; potassium carbonate; triphenylphosphine In 5,5-dimethyl-1,3-cyclohexadiene at 150℃; for 24h; Inert atmosphere;
52% With sodium hydroxide; potassium carbonate; methanesulfonyl chloride In benzene for 1h; Heating;
35% With potassium <i>tert</i>-butylate; copper diacetate In toluene at 150℃; for 240h; Inert atmosphere; Neat (no solvent); 4.4. General procedure for synthesis of amides 12, 14 and 16 General procedure: To a solution of Cu(OAc)2 (0.05 mmol, 0.0092 g) and potassium tert-butoxide (0.175 g, 2.5 mmol) in anhydrous dioxane (3 mL), the corresponding amide 11, 13 or 15 (2.5 mmol) and the corresponding alcohol 2 (3.25 mmol) were added successively under inert argon atmosphere. After 5 days of reaction at 150 °C, it was hydrolyzed with a saturated solution of ammonium chloride (10 mL). The mixture was extracted with AcOEt (3×10 mL) and washed with brine (10 mL), after drying over anhydrous MgSO4 and filtering on Celite, the solvents were removed under low pressure (15-18 Torr). The resulting mixture was purified by column chromatography (if needed).
With silver hexafluoroantimonate In water at 110℃; for 16h;

  • 8
  • [ 1079-66-9 ]
  • [ 5994-87-6 ]
YieldReaction ConditionsOperation in experiment
97% Stage #1: chloro-diphenylphosphine With triethylamine; acetone oxime In dichloromethane at -70 - 20℃; Stage #2: With ammonium hydroxide for 0.75h;
97% With triethylamine; acetone oxime In dichloromethane at -78 - 20℃; for 2.75h; Inert atmosphere;
Multi-step reaction with 3 steps 1: alkaline hydrogen peroxide 2: thionyl chloride / benzene / 2 h / Heating 3: 4 M ethanolic ammonia / CH2Cl2 / Ambient temperature
Multi-step reaction with 2 steps 1: Et3N / CH2Cl2; petroleum ether 2: H2O / tetrahydrofuran
Multi-step reaction with 2 steps 1: Et3N / CH2Cl2; petroleum ether 2: H2O / tetrahydrofuran
Multi-step reaction with 6 steps 1: sulfur / toluene / 4.5 h / Heating 2: triethylamine / dichloromethane / 1.) ice-cooled, 15 min, 2.) r.t., overnight 3: methanol / 1.5 h 4: triethylamine / dichloromethane / 0.08 h 5: dichloromethane 6: sodium methylate / methanol / 0.2 h
Multi-step reaction with 6 steps 1: sulfur / toluene / 4.5 h / Heating 2: triethylamine / dichloromethane / 1.) ice-cooled, 15 min, 2.) r.t., overnight 3: methanol / 1.5 h 4: triethylamine / dichloromethane / 0.08 h 5: sodium methylate / methanol / 0.05 h / 5 °C 6: sodium methylate / methanol / 0.2 h
Multi-step reaction with 6 steps 1: sulfur / toluene / 4.5 h / Heating 2: triethylamine / dichloromethane / 1.) ice-cooled, 15 min, 2.) r.t., overnight 3: methanol / 1.5 h 4: triethylamine / dichloromethane / 0.08 h 5: <i>tert</i>-butylamine / dichloromethane 6: sodium methylate / methanol / 0.2 h
Multi-step reaction with 2 steps 1: ammonia / dichloromethane / 1.25 h / -45 - 20 °C / Inert atmosphere 2: dihydrogen peroxide / dichloromethane; water / 1.5 h / Cooling with ice

  • 10
  • [ 5994-87-6 ]
  • [ 15174-47-7 ]
  • N-((E)-2-methyl-3-phenylallylidene)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
46% With titanium tetrachloride; triethylamine In dichloromethane at 20℃; for 1h;
With titanium tetrachloride; triethylamine In dichloromethane at 5 - 22℃; for 1h;
  • 11
  • [ 1736-06-7 ]
  • [ 5994-87-6 ]
  • [ 3087-36-3 ]
  • [ 902453-29-6 ]
  • 12
  • [ 5994-87-6 ]
  • [ 321-37-9 ]
  • [ 3087-36-3 ]
  • [ 902453-32-1 ]
  • 13
  • [ 5994-87-6 ]
  • C48H51N6O7PS [ No CAS ]
YieldReaction ConditionsOperation in experiment
41% Stage #1: C36H41N5O7S With 1,1'-carbonyldiimidazole In dichloromethane at 45℃; for 1h; Stage #2: diphenylphosphinamide In dichloromethane at 20 - 45℃; for 3h; 1.2E In a one dram vial, carboxylic acid 2a (0.015 g, 0.022 mmol) was dissolved in 0.75 mL DCM, then treated with CDI (5.3 mg, 0.033 mmol). The resulting mixture was then moved to a 45° C. oil bath and stirred for 1 h. After cooling to rt, the vial was opened and diphenylphosphinamide (14.3 mg, 0.066 mmol) was added. The vial was then purged N2, capped, and moved back to the 45° C. oil bath, where it was stirred for 3 h. After cooling, the reaction mixture was loaded directly onto a plug of SiO2 and purified via flash chromatography using EtOAc in hexanes (20%→50%→95%) to yield the title compound, (8.0 mg, 41%) as a white solid.MS (ESI) m/z=887.3 (M+H)+.
  • 14
  • [ 5994-87-6 ]
  • [ 459-57-4 ]
  • P,P-diphenyl-N-(4-fluorophenylmethylene)phosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
54% With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;
45% With titanium(IV) tetraethanolate In tetrahydrofuran Reflux; General procedure A for the preparation of diphenylphosphinoyl benzaldimines 1a-j: General procedure: In a flame-dried two-neck round-bottom flask, diphenylphosphinic amide (0.66 g, 3.0 mmol) was added to a stirred solution of aldehyde (3.3 mmol) and Ti(OEt)4 (1.28 mL, 6.0 mmol) in THF (8.5 mL). The solution was stirred under reflux for 1-3 h depending on the substrate. The reaction was monitored by TLC until completion, the solution allowed to cool down to room temperature and the solvent evaporated. The mixture was dissolved in dichloromethane and then filtered through a pad of celite and rinsed with dichloromethane. The organic extract is concentrated to a cream solid and purified by flash chromatography column. The crude product (which is not fully soluble in the initial chromatographic eluent) was transferred as a suspension to the top of a 4 cm diameter x 9 cm high silica column using 6:4 EtOAc:Pentane. Elution with the same solvent system gave residual aldehyde. Continued elution with EtOAc afforded the product as a white solid. Yields obtained were within the range of 40-70%. Lower yields were associated with slower elution of the products and occasionally batches of over activated silica.
With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;
With pyrrolidine In dichloromethane for 16h; Molecular sieve; Reflux;
With pyrrolidine In dichloromethane at 65℃; for 24h; Molecular sieve;
With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;

  • 15
  • [ 455-19-6 ]
  • [ 5994-87-6 ]
  • [ 207222-25-1 ]
YieldReaction ConditionsOperation in experiment
30% With titanium(IV) tetraethanolate In tetrahydrofuran Reflux; General procedure A for the preparation of diphenylphosphinoyl benzaldimines 1a-j: General procedure: In a flame-dried two-neck round-bottom flask, diphenylphosphinic amide (0.66 g, 3.0 mmol) was added to a stirred solution of aldehyde (3.3 mmol) and Ti(OEt)4 (1.28 mL, 6.0 mmol) in THF (8.5 mL). The solution was stirred under reflux for 1-3 h depending on the substrate. The reaction was monitored by TLC until completion, the solution allowed to cool down to room temperature and the solvent evaporated. The mixture was dissolved in dichloromethane and then filtered through a pad of celite and rinsed with dichloromethane. The organic extract is concentrated to a cream solid and purified by flash chromatography column. The crude product (which is not fully soluble in the initial chromatographic eluent) was transferred as a suspension to the top of a 4 cm diameter x 9 cm high silica column using 6:4 EtOAc:Pentane. Elution with the same solvent system gave residual aldehyde. Continued elution with EtOAc afforded the product as a white solid. Yields obtained were within the range of 40-70%. Lower yields were associated with slower elution of the products and occasionally batches of over activated silica.
With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;
With pyrrolidine In dichloromethane at 65℃; for 24h; Molecular sieve;
With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;

  • 16
  • [ 5994-87-6 ]
  • [ 104-87-0 ]
  • N-(4-methylbenzylidene)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% With titanium(IV) tetraethanolate In tetrahydrofuran Reflux; General procedure A for the preparation of diphenylphosphinoyl benzaldimines 1a-j: General procedure: In a flame-dried two-neck round-bottom flask, diphenylphosphinic amide (0.66 g, 3.0 mmol) was added to a stirred solution of aldehyde (3.3 mmol) and Ti(OEt)4 (1.28 mL, 6.0 mmol) in THF (8.5 mL). The solution was stirred under reflux for 1-3 h depending on the substrate. The reaction was monitored by TLC until completion, the solution allowed to cool down to room temperature and the solvent evaporated. The mixture was dissolved in dichloromethane and then filtered through a pad of celite and rinsed with dichloromethane. The organic extract is concentrated to a cream solid and purified by flash chromatography column. The crude product (which is not fully soluble in the initial chromatographic eluent) was transferred as a suspension to the top of a 4 cm diameter x 9 cm high silica column using 6:4 EtOAc:Pentane. Elution with the same solvent system gave residual aldehyde. Continued elution with EtOAc afforded the product as a white solid. Yields obtained were within the range of 40-70%. Lower yields were associated with slower elution of the products and occasionally batches of over activated silica.
With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;
With pyrrolidine In dichloromethane for 16h; Molecular sieve; Reflux;
  • 17
  • [ 5994-87-6 ]
  • [ 529-20-4 ]
  • N-(2-methylbenzylidene)-P,P-diphenylphosphinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
56% With titanium(IV) tetraethanolate In tetrahydrofuran Reflux; General procedure A for the preparation of diphenylphosphinoyl benzaldimines 1a-j: General procedure: In a flame-dried two-neck round-bottom flask, diphenylphosphinic amide (0.66 g, 3.0 mmol) was added to a stirred solution of aldehyde (3.3 mmol) and Ti(OEt)4 (1.28 mL, 6.0 mmol) in THF (8.5 mL). The solution was stirred under reflux for 1-3 h depending on the substrate. The reaction was monitored by TLC until completion, the solution allowed to cool down to room temperature and the solvent evaporated. The mixture was dissolved in dichloromethane and then filtered through a pad of celite and rinsed with dichloromethane. The organic extract is concentrated to a cream solid and purified by flash chromatography column. The crude product (which is not fully soluble in the initial chromatographic eluent) was transferred as a suspension to the top of a 4 cm diameter x 9 cm high silica column using 6:4 EtOAc:Pentane. Elution with the same solvent system gave residual aldehyde. Continued elution with EtOAc afforded the product as a white solid. Yields obtained were within the range of 40-70%. Lower yields were associated with slower elution of the products and occasionally batches of over activated silica.
With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;
With titanium tetrachloride Inert atmosphere;
With pyrrolidine In dichloromethane at 65℃; for 24h; Molecular sieve;
With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;

  • 18
  • [ 5994-87-6 ]
  • [ 620-23-5 ]
  • N-(3-methylbenzylidene)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
71% With titanium(IV) tetraethanolate In tetrahydrofuran Reflux; General procedure A for the preparation of diphenylphosphinoyl benzaldimines 1a-j: General procedure: In a flame-dried two-neck round-bottom flask, diphenylphosphinic amide (0.66 g, 3.0 mmol) was added to a stirred solution of aldehyde (3.3 mmol) and Ti(OEt)4 (1.28 mL, 6.0 mmol) in THF (8.5 mL). The solution was stirred under reflux for 1-3 h depending on the substrate. The reaction was monitored by TLC until completion, the solution allowed to cool down to room temperature and the solvent evaporated. The mixture was dissolved in dichloromethane and then filtered through a pad of celite and rinsed with dichloromethane. The organic extract is concentrated to a cream solid and purified by flash chromatography column. The crude product (which is not fully soluble in the initial chromatographic eluent) was transferred as a suspension to the top of a 4 cm diameter x 9 cm high silica column using 6:4 EtOAc:Pentane. Elution with the same solvent system gave residual aldehyde. Continued elution with EtOAc afforded the product as a white solid. Yields obtained were within the range of 40-70%. Lower yields were associated with slower elution of the products and occasionally batches of over activated silica.
With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;
With pyrrolidine In dichloromethane for 16h; Molecular sieve; Reflux;
  • 19
  • [ 111-70-6 ]
  • [ 5994-87-6 ]
  • [ 1301628-39-6 ]
YieldReaction ConditionsOperation in experiment
17% With potassium <i>tert</i>-butylate; copper diacetate In toluene at 150℃; for 240h; Inert atmosphere; Neat (no solvent); 4.4. General procedure for synthesis of amides 12, 14 and 16 General procedure: To a solution of Cu(OAc)2 (0.05 mmol, 0.0092 g) and potassium tert-butoxide (0.175 g, 2.5 mmol) in anhydrous dioxane (3 mL), the corresponding amide 11, 13 or 15 (2.5 mmol) and the corresponding alcohol 2 (3.25 mmol) were added successively under inert argon atmosphere. After 5 days of reaction at 150 °C, it was hydrolyzed with a saturated solution of ammonium chloride (10 mL). The mixture was extracted with AcOEt (3×10 mL) and washed with brine (10 mL), after drying over anhydrous MgSO4 and filtering on Celite, the solvents were removed under low pressure (15-18 Torr). The resulting mixture was purified by column chromatography (if needed).
  • 20
  • [ 5994-87-6 ]
  • [ 90134-10-4 ]
  • (E)-N-(4-(dibutylamino)benzylidene)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With titanium tetrachloride; triethylamine; In dichloromethane; at -78 - 22℃; for 12h;Inert atmosphere; General procedure: [00236] General Procedure for Preparation of Ar l.-, Heteroaryl-, Alkenyl-, md Alkyayl Aldimines (3|): AJdimine 3j was prepared following a modified reported procedure, A flame-dried 100 mL round-bottom flask, purged with nitrogen, is charged with 4-(dibutylamino) benzaldehyde (5.51 gs 23.6 mmol, 1.25 equiv.), P,F-diphenylphosphinic amide (4,10 g, 18.9 mmol, 1.00 equiv.), triethylamine (10.6 mL, 75.6 mmol, 4.00 equiv.), and dichloromethane (60 mL). The resulting mixture is allowed to cool to -78 C, followed by the drop-wise addition of neat TiCl4 (1.14 mL, 10.4 mmol, 0.55 equiv.). The solution is allowed to stir for 12 h at 22 C and is then filtered through a plug of Celite. The resulting yellow solid is purified by silica gel column chromatography (ethyl acetate:hexanes 2: 1 followed by 100% ethyl acetate as eluent) and recrystallized from dichloromethane/hexanes to afford 3j as pale yellow solid (6.40 g, 14.8 mmol, 78% yield). [00237] (E)- V-(4-(dibutylamino)benzylidene)- , -diphenylphosphinic amide (3j): M.p. = 1 13-1 15 C. IR (neat): 2951 (w), 2928 (w), 2869 (w), 1579 (m), 1525 (m), 1435 (m), 1364 (m), 1203 (m), 1 173 (m), 1 104 (m), 831 (s), 807 (m), 725 (m), 695 (s), 580 (m), 545 (s), 522 (s), 510 (s) cm"1; 1H NMR (400 MHz, CDC13): delta 9.08 (1H, d, J = 32.0 Hz), 7.95-7.89 (4H, m), 7.85 (2H, d, J = 8.8 Hz), 7.48-7.38 (6H, m), 6.65 (2H, d, J = 9.2 Hz), 3.34 (4H, dd, J = 7.6, 7.2 Hz), 1.63-1.56 (4H, m), 1.37 (4H, app sextet, J= 7.6 Hz), 0.97 (6H, t, J= 7.2 Hz); 13C NMR (100 MHz, CDC13): delta 172.1 (d, J= 6.9 Hz), 152.3, 134.4 (d, J= 126.0 Hz), 132.7 (br peak as the result of hindered rotation around the (Ar)-(C=NR) bond), 131.7 (d, J = 9.1 Hz), 131.4 (d, J = 2.7 Hz), 128.4 (d, J = 12.3 Hz), 123.5 (d, J = 26.2 Hz), 1 1 1.0, 51.0, 29.4, 20.4, 14.1 ; HRMS Calcd for C27H34N2OP [M + H]+: 433.24087; Found: 433.23945.
  • 21
  • [ 5994-87-6 ]
  • [ 104-15-4 ]
  • [ 156939-62-7 ]
  • [ 1566557-36-5 ]
  • 22
  • [ 5994-87-6 ]
  • [ 105-07-7 ]
  • N-(4-cyanobenzylidene)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
74% With titanium(IV) tetraethanolate In tetrahydrofuran Reflux; General procedure A for the preparation of diphenylphosphinoyl benzaldimines 1a-j: General procedure: In a flame-dried two-neck round-bottom flask, diphenylphosphinic amide (0.66 g, 3.0 mmol) was added to a stirred solution of aldehyde (3.3 mmol) and Ti(OEt)4 (1.28 mL, 6.0 mmol) in THF (8.5 mL). The solution was stirred under reflux for 1-3 h depending on the substrate. The reaction was monitored by TLC until completion, the solution allowed to cool down to room temperature and the solvent evaporated. The mixture was dissolved in dichloromethane and then filtered through a pad of celite and rinsed with dichloromethane. The organic extract is concentrated to a cream solid and purified by flash chromatography column. The crude product (which is not fully soluble in the initial chromatographic eluent) was transferred as a suspension to the top of a 4 cm diameter x 9 cm high silica column using 6:4 EtOAc:Pentane. Elution with the same solvent system gave residual aldehyde. Continued elution with EtOAc afforded the product as a white solid. Yields obtained were within the range of 40-70%. Lower yields were associated with slower elution of the products and occasionally batches of over activated silica.
With pyrrolidine In dichloromethane at 65℃; for 24h; Molecular sieve;
With titanium tetrachloride; triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;
  • 23
  • [ 939-97-9 ]
  • [ 5994-87-6 ]
  • N-(4-(tert-butyl)benzylidene)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
94% With titanium(IV) tetraethanolate In tetrahydrofuran Reflux; General procedure A for the preparation of diphenylphosphinoyl benzaldimines 1a-j: General procedure: In a flame-dried two-neck round-bottom flask, diphenylphosphinic amide (0.66 g, 3.0 mmol) was added to a stirred solution of aldehyde (3.3 mmol) and Ti(OEt)4 (1.28 mL, 6.0 mmol) in THF (8.5 mL). The solution was stirred under reflux for 1-3 h depending on the substrate. The reaction was monitored by TLC until completion, the solution allowed to cool down to room temperature and the solvent evaporated. The mixture was dissolved in dichloromethane and then filtered through a pad of celite and rinsed with dichloromethane. The organic extract is concentrated to a cream solid and purified by flash chromatography column. The crude product (which is not fully soluble in the initial chromatographic eluent) was transferred as a suspension to the top of a 4 cm diameter x 9 cm high silica column using 6:4 EtOAc:Pentane. Elution with the same solvent system gave residual aldehyde. Continued elution with EtOAc afforded the product as a white solid. Yields obtained were within the range of 40-70%. Lower yields were associated with slower elution of the products and occasionally batches of over activated silica.
  • 24
  • [ 5994-87-6 ]
  • [ 1571-08-0 ]
  • methyl (E)-4-(((diphenylphosphoryl)imino)methyl)benzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With tris(2,2,2-trifluoroethyl) borate In chloroform at 20℃; for 24h; Inert atmosphere;
70% With pyrrolidine In dichloromethane at 15 - 65℃; for 24h; Inert atmosphere; 1.1-c Step 1-c: Preparation of Methyl (E)-4-(((diphenylphosphoryl)imino)methyl)benzoate (G) To a solution of Methyl 4-formylbenzoate (50 g) in DCM (1 L) under N2 atmosphere at 15-35 oC, P,P-diphenylphosphinic amide (66 g, 1 equiv.) and 4 Å MS (250 g) was added, then pyrrolidine (4.3 g, 0.2 equiv.) was added finally. The mixture was stirred at 65 oC for 24 h. Upon cooling to room temperature, the reaction was filtered and the filtrate was dried by vapor. Then the residue was purified by silica gel chromatography to afford Compound G (77 g, 70%) as a white solid.
  • 26
  • [ 5994-87-6 ]
  • [ 5720-05-8 ]
  • [ 36163-88-9 ]
YieldReaction ConditionsOperation in experiment
85% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 27
  • [ 5994-87-6 ]
  • [ 98-80-6 ]
  • [ 6190-28-9 ]
YieldReaction ConditionsOperation in experiment
76% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 28
  • [ 5994-87-6 ]
  • [ 16419-60-6 ]
  • P,P-diphenyl-N-(o-tolyl) phosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 29
  • [ 5994-87-6 ]
  • [ 17933-03-8 ]
  • [ 38938-21-5 ]
YieldReaction ConditionsOperation in experiment
79% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 30
  • [ 5994-87-6 ]
  • [ 55499-44-0 ]
  • P,P-diphenyl-N-(2,4-dimethylphenyl) phosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With copper diacetate; caesium carbonate; In toluene; at 80℃; for 10h;Molecular sieve; General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4AMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80C (120C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 31
  • [ 5994-87-6 ]
  • [ 90002-36-1 ]
  • P,P-diphenyl-N-(2-ethylphenyl) phosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% With copper diacetate; caesium carbonate; In toluene; at 80℃; for 10h;Molecular sieve; General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4AMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80C (120C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 32
  • [ 5994-87-6 ]
  • [ 63139-21-9 ]
  • P,P-diphenyl-N-(4-ethylphenyl) phosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
79% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 33
  • [ 5994-87-6 ]
  • [ 16152-51-5 ]
  • [ 1224839-45-5 ]
YieldReaction ConditionsOperation in experiment
75% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 34
  • [ 5994-87-6 ]
  • [ 123324-71-0 ]
  • N-(4-(tert-butyl)phenyl)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 35
  • [ 5994-87-6 ]
  • [ 10365-98-7 ]
  • P,P-diphenyl-N-(3-methoxyphenyl) phosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
79% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 36
  • [ 5994-87-6 ]
  • [ 5720-07-0 ]
  • [ 29882-18-6 ]
YieldReaction ConditionsOperation in experiment
83% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 37
  • [ 5994-87-6 ]
  • [ 1765-93-1 ]
  • [ 72358-69-1 ]
YieldReaction ConditionsOperation in experiment
80% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 38
  • [ 5994-87-6 ]
  • [ 1679-18-1 ]
  • [ 7473-27-0 ]
YieldReaction ConditionsOperation in experiment
75% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 39
  • [ 5994-87-6 ]
  • [ 5467-74-3 ]
  • [ 101318-12-1 ]
YieldReaction ConditionsOperation in experiment
70% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 40
  • [ 5994-87-6 ]
  • [ 128796-39-4 ]
  • P,P-diphenyl-N-(4-(trifluoromethyl)phenyl) phosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 41
  • [ 5994-87-6 ]
  • [ 5570-19-4 ]
  • P,P-diphenyl-N-(2-nitrophenyl) phosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
65% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 42
  • [ 5994-87-6 ]
  • [ 13922-41-3 ]
  • [ 105976-12-3 ]
YieldReaction ConditionsOperation in experiment
76% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 43
  • [ 5994-87-6 ]
  • [ 197958-29-5 ]
  • [ 41049-57-4 ]
YieldReaction ConditionsOperation in experiment
46% With copper diacetate; caesium carbonate In toluene at 80℃; for 10h; Molecular sieve; 4.2.1 Procedures towards N-aryl phosphonic/phosphinic amides General procedure: A Schlenk tube (35mL) equipped with a magnetic bar was loaded with the phosphonamides or phosphinamides 1 (0.5mmol) and Cu(OAc)2 (181mg, 1.0mmol) in dry toluene (3.5mL), then arylboronic acids 2 (0.6mmol, 1.2 equiv.), Cs2CO3 (1.0mmol, 2.0 equiv.) and 4ÅMS (100wt%) were added in portions and the reaction mixture was allowed to stir at 80°C (120°C for 4aa) for 10h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15mL×3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and a petroleum ether and ethyl acetate (3/1) as eluent to give the N-aryl phosphonamides or phosphinamides 3 and 4aa (in sealed tube) in noted yields.
  • 44
  • [ 536-57-2 ]
  • [ 5994-87-6 ]
  • [ 100-52-7 ]
  • [ 701291-86-3 ]
YieldReaction ConditionsOperation in experiment
91% In diethyl ether; dichloromethane at 20℃; for 48h;
  • 45
  • [ 5994-87-6 ]
  • [ 73960-07-3 ]
  • (E)-N-(4-(difluoromethoxy)benzylidene)-P,P-diphenylphosphinic amide [ No CAS ]
  • 46
  • [ 5994-87-6 ]
  • [ 73960-07-3 ]
  • N-((1S,2R)-1-(4-(difluoromethoxy)phenyl)-2-((diphenylmethylene)amino)propy-l)-P,P-diphenylphosphinic amide [ No CAS ]
  • 47
  • [ 95-47-6 ]
  • [ 5994-87-6 ]
  • [ 1224953-93-8 ]
YieldReaction ConditionsOperation in experiment
83% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
82% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 16 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 48
  • [ 5994-87-6 ]
  • [ 108-38-3 ]
  • N-(3-methylbenzyl)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
87% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 17 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 49
  • [ 106-42-3 ]
  • [ 5994-87-6 ]
  • N-(4-methylbenzyl)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
86% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 18 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 50
  • [ 5994-87-6 ]
  • [ 108-67-8 ]
  • N-(3,5-dimethylbenzyl)-P,P-diphenyl-phosphinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
82% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 19 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 51
  • [ 5994-87-6 ]
  • [ 98-51-1 ]
  • N-(4-(tert-butyl)benzyl)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 20 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
80% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
  • 52
  • [ 352-32-9 ]
  • [ 5994-87-6 ]
  • [ 850791-26-3 ]
YieldReaction ConditionsOperation in experiment
84% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
83% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 22 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 53
  • [ 95-49-8 ]
  • [ 5994-87-6 ]
  • N-(2-chlorobenzyl)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
84% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 23 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 54
  • [ 108-41-8 ]
  • [ 5994-87-6 ]
  • [ 1224953-91-6 ]
YieldReaction ConditionsOperation in experiment
82% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
80% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 24 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 55
  • [ 106-43-4 ]
  • [ 5994-87-6 ]
  • N-(4-chlorobenzyl)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
87% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 25 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 56
  • [ 6140-17-6 ]
  • [ 5994-87-6 ]
  • P,P-diphenyl-N-(4-(trifluoromethyl)benzyl)phosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide; at 120℃; for 36h;Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4A, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 57
  • [ 99-75-2 ]
  • [ 5994-87-6 ]
  • methyl 4-(((diphenylphosphoryl)amino)methyl)benzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 28 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 58
  • [ 101-81-5 ]
  • [ 5994-87-6 ]
  • [ 71847-25-1 ]
YieldReaction ConditionsOperation in experiment
82% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
78% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide In chloroform at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 32 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 59
  • [ 5994-87-6 ]
  • [ 4957-14-6 ]
  • N-(di-p-tolylmethyl)-P,P-diphenyl-phosphinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
72% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide In chloroform at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 44 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 60
  • [ 5994-87-6 ]
  • [ 726-18-1 ]
  • N-(di-4-methoxyphenylmethyl)-P,P-diphenyl-phosphinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
72% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
68% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide In chloroform at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 45 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 61
  • [ 5994-87-6 ]
  • [ 457-68-1 ]
  • N-[di-(4-fluorophenyl)methyl]-P,P-diphenyl-phosphinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
65% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide In chloroform at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 46 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 62
  • [ 5994-87-6 ]
  • [ 713-36-0 ]
  • N-[phenyl(o-tolyl)methyl]-P,P-diphenyl-phosphinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
70% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide In chloroform at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 47 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 63
  • [ 620-47-3 ]
  • [ 5994-87-6 ]
  • N-[phenyl(m-tolyl)methyl]-P,P-diphenyl-phosphinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
71% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide In chloroform at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 48 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 64
  • [ 5994-87-6 ]
  • [ 620-83-7 ]
  • P,P-diphenyl-N-(4-methyl-α-phenylbenzyl)phosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
73% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide In chloroform at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 49 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
73% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
  • 65
  • [ 5994-87-6 ]
  • [ 834-14-0 ]
  • N-[(4-methoxyphenyl)(phenyl)methyl]-P,P-diphenyl-phosphinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
65% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide In chloroform at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 50 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 66
  • [ 587-79-1 ]
  • [ 5994-87-6 ]
  • N-[(4-fluorophenyl)(phenyl)methyl]-P,P-diphenyl-phosphinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
66% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
63% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide In chloroform at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 51 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 67
  • [ 831-81-2 ]
  • [ 5994-87-6 ]
  • [ 847049-46-1 ]
YieldReaction ConditionsOperation in experiment
67% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide; In chloroform; at 120℃; for 36h;Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4A, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 68
  • [ 2116-36-1 ]
  • [ 5994-87-6 ]
  • N-[(4-bromophenyl)(phenyl)methyl]-P,P-diphenyl-phosphinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
65% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide In chloroform at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 53 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
65% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
  • 69
  • [ 5994-87-6 ]
  • [ 34239-04-8 ]
  • N-[(phenyl)(4-trifluoromethylphenyl)methyl]-P,P-diphenyl-phosphinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
62% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
58% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide In chloroform at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 54 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
  • 70
  • [ 39768-70-2 ]
  • [ 5994-87-6 ]
  • N-[(4-fluorophenyl)(p-tolyl)methyl]-P,P-diphenyl-phosphinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide; cobalt(II) bromide In chloroform at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube; 55 4.2.1. Procedures towards N-benzyl phosphorylamides 3 (5) General procedure: Under the argon stomosphere, a Schlenk tube (35 mL) equipped with a magnetic bar was charged with a solution of 1 (0.5 mmol), MS (4Å, powdered, 200 wt%), CoBr2 (10 mol%), AIBN (0.2 equiv.) in 2 or 4 (5.0 mL, ca. 30 equiv.), then DTBP (2.0 equiv.) was added dropwise to the system and the mixture was allowed to stir at 120 °C for 36 h. After cooling to room temperature, the mixture was filtered through a short celite pad and washed with dichloromethane (15 mL * 3). The filtrate was concentrated and the oily crude product was purified by column chromatography using silica gel (200-300 mesh) as stationary phase and ethyl acetate as eluent to give the corresponding products 3 or 5 in noted yields.
70% With copper(l) iodide; 2,2'-azobis(isobutyronitrile); di-tert-butyl peroxide at 120℃; for 36h; Inert atmosphere; Schlenk technique; Molecular sieve; Sealed tube;
  • 71
  • [ 5994-87-6 ]
  • [ 2840-44-0 ]
  • C22H19FNOP [ No CAS ]
  • 72
  • [ 5994-87-6 ]
  • [ 2840-44-0 ]
  • (R)-7-fluoro-1-tetralinyldiphenylphosphinamide [ No CAS ]
  • 73
  • [ 928-91-6 ]
  • [ 5994-87-6 ]
  • (Z)-N-(hex-4-en-1-yl)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
95% With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide In toluene at 110℃; for 16h; Inert atmosphere; Sealed tube; Glovebox; chemoselective reaction; 4.1. General Procedures General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.
  • 74
  • [ 7540-51-4 ]
  • [ 5994-87-6 ]
  • (S)-N-(3,7-dimethyloct-6-en-1-yl)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
98% With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide In toluene at 110℃; for 16h; Inert atmosphere; Sealed tube; Glovebox; chemoselective reaction; 4.1. General Procedures General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.
  • 75
  • [ 2516-33-8 ]
  • [ 5994-87-6 ]
  • [ 68036-36-2 ]
YieldReaction ConditionsOperation in experiment
93% With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide In toluene at 110℃; for 16h; Inert atmosphere; Sealed tube; Glovebox; 4.1. General Procedures General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.
89% With potassium hydroxide In toluene at 110℃; for 4h;
  • 76
  • [ 1592-38-7 ]
  • [ 5994-87-6 ]
  • N-(naphthalen-2-ylmethyl)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
99% With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide In toluene at 110℃; for 16h; Inert atmosphere; Sealed tube; Glovebox; 4.1. General Procedures General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.
92% With potassium hydroxide In toluene at 110℃; for 4h;
  • 77
  • [ 5994-87-6 ]
  • [ 636-72-6 ]
  • [ 1283087-86-4 ]
YieldReaction ConditionsOperation in experiment
98% With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide In toluene at 110℃; for 16h; Inert atmosphere; Sealed tube; Glovebox; 4.1. General Procedures General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.
92% With potassium hydroxide In toluene at 110℃; for 4h;
  • 78
  • [ 586-95-8 ]
  • [ 5994-87-6 ]
  • P,P-diphenyl-N-(pyridin-4-ylmethyl)phosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide In toluene at 110℃; for 16h; Inert atmosphere; Sealed tube; Glovebox; 4.1. General Procedures General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.
  • 79
  • [ 586-98-1 ]
  • [ 5994-87-6 ]
  • P,P-diphenyl-N-(pyridin-2-ylmethyl)phosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
99% With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide In toluene at 110℃; for 16h; Inert atmosphere; Sealed tube; Glovebox; 4.1. General Procedures General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.
84% With potassium hydroxide In toluene at 110℃; for 4h;
  • 80
  • [ 5994-87-6 ]
  • [ 25193-95-7 ]
  • P,P-diphenyl-N-(pyrimidin-5-ylmethyl)phosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
72% With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide; In toluene; at 110℃; for 16h;Inert atmosphere; Sealed tube; Glovebox; General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.
  • 81
  • [ 5994-87-6 ]
  • [ 17849-38-6 ]
  • N-(2-chlorobenzyl)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
92% With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide In toluene at 110℃; for 16h; Inert atmosphere; Sealed tube; Glovebox; 4.1. General Procedures General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.
88% With potassium hydroxide In toluene at 110℃; for 4h;
  • 82
  • [ 89-95-2 ]
  • [ 5994-87-6 ]
  • [ 1224953-93-8 ]
YieldReaction ConditionsOperation in experiment
86% With potassium hydroxide In toluene at 110℃; for 4h;
79% With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide In toluene at 110℃; for 16h; Inert atmosphere; Sealed tube; Glovebox; 4.1. General Procedures General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.
  • 83
  • [ 5994-87-6 ]
  • [ 446-51-5 ]
  • N-(2-fluorobenzyl)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide; In toluene; at 110℃; for 16h;Inert atmosphere; Sealed tube; Glovebox; General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.
  • 84
  • [ 5994-87-6 ]
  • [ 6971-51-3 ]
  • N-(3-methoxybenzyl)-P,P-diphenylphosphinic amide [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)-amino]ruthenium(II); potassium hydroxide In toluene at 110℃; for 16h; Inert atmosphere; Sealed tube; Glovebox; 4.1. General Procedures General procedure: Glovebox Procedure (General Procedure 1): Inside an argonfilled glovebox (O2 levels between 35.0 and 55.0 ppm, H2O levels unknown), to an oven dried 10-mL screw cap vial equipped with a Teflon-coated magnetic stir bar were added Ru-MACHO (1.2 mg, 2.00 mmol), KOH (1.7 mg, 30.0 mmol), and the appropriate phosphinic amide (0.200 mmol) in that order. Subsequently, toluene (0.7 mL) was added via micropipette, with care taken to ensure that solids on the wall were washed to the bottom of the vial. Next, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The reaction was sealed tightly with a non-puncturable cap and was further sealed by placing a piece of electrical tape around the cap and top of vial. Schlenk Line Procedure (General Procedure 2): To a flame-dried vial were quickly added Ru-MACHO (1.2 mg, 2.00 mmol) and KOH (1.7 mg, 30.0 mmol) (stored under Ar) (addition time 1 min), and the reaction vial was left open under a steady flow of nitrogen (applied via a needle placed at the top of the vial). Next, the appropriate phosphinic amide (0.200 mmol) was added, followed by the addition of toluene (0.7 mL) from a standard Solvent Purification System (SPS). Lastly, the appropriate alcohol (0.240 mmol) was added either as a solid or via micropipette for liquid substrates. The nitrogen line was removed, and the vial was then quickly and tightly sealed with a non-puncturable cap and further sealed by placing a piece of electrical tape around the cap and top of the vial. After the differing series of operations described above, General Procedures 1 and 2 then followed then same protocol. The reaction vessel was placed in a preheated oil bath at 110e140 C with a stirring rate of 500 rpm. As the reaction was proceeding, the vessel was periodically visually monitored. If large amounts of solid were found to have accumulated on the wall, the vial was briefly removed from the oil bath and shaken to wash the solids back to the bottom of the vial. After 16 h, the vial was removed from the oil bath and allowed to cool to room temperature. Methanol (1 mL) was added to dissolve all solids, and the solvent removed in vacuo. The solid was redissolved in methanol (1 mL), and the solution was filtered through a 40-mm syringe filter. Samples were then purified by reverse-phase HPLC or recrystallized from hot benzene. In the case of HPLC purification, the fractions were combined, frozen in liquid N2, and lyophilized to sublime the solvent.
Same Skeleton Products
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