Name: 52409-22-0|Pd2(DBA)3|98%
Brand: Ambeed
SKU: A172297
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1
[ 153254-09-2 ]
[ 52409-22-0 ]
di-tert-butyl-trimethylsilanylmethyl-phosphine [ No CAS ]
[ 81-29-8 ]
[ 868555-70-8 ]

Yield	Reaction Conditions	Operation in experiment
	With caesium carbonate; In 1,4-dioxane; water;	Example 2 1,3,6,8-Tetrakis-(2,4-bis-trifluoromethyl-phenyl)-pyrene 3.95 g (0.0116 mol) of 1,3,6,8-tetrachloro-pyrene, 15.0 g (0.0582 mol) of <strong>[153254-09-2]2,4-bis(trifluoromethyl)phenylboronic acid</strong>, 1.33 g (0.00145 mol) of tris(dibenzylideneacetone) dipalladium (0), 0.64 g (0.00276 mol) of di-tert-butyl-trimethylsilylmethyl-phosphane, 18.95 g (0.0582 mol) of cesium carbonate and 100 ml of dioxane were stirred at room temperature for 24 hours. The resultant mixture was poured into 200 ml of water and extracted twice with 200 ml of methylene chloride. The organic phase was dried over magnesium sulfate overnight and filtered. The solvent was removed on a roto-evaporator and the residue was purified by chromatography on silica gel with petroleum ether/ethyl ether (10/0.5) as eluent. Yield of 1,3,6,8-tetrakis-(2,4-bis-trifluoromethyl-phenyl)-pyrene: 1.08 g (8.85%) as a white solid with m.p. 290.00 C. 1H NMR (CDCl3) 7.45-8.30 (multiplets, 18H, arom-H). 19F NMR (CDCl3) -59.16, -63.27. The structure was confirmed by X-ray analysis.

Reference： [1]Patent: US2005/244645,2005,A1

2
[ 52409-22-0 ]
(RR,SS)-3-(2-methoxyphenyl)-2-methyl-3-(1-naphthyl)-2-(piperazin-1-ylcarbonyl)propanenitrile [ No CAS ]
[ 2252-44-0 ]
(RR,SS)-3-(2-methoxyphenyl)-2-methyl-3-(1-naphthyl)-2-({4-[3-(trifluoromethoxy)phenyl]piperazin-1-yl}carbonyl)propanenitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium t-butanolate; In diethyl ether; toluene;	EXAMPLE 92 (RR,SS)-3-(2-methoxyphenyl)-2-methyl-3-(1-naphthyl)-2-({4-[3-(trifluoromethoxy)phenyl]piperazin-1-yl}carbonyl)propanenitrile (RR,SS)-3-(2-methoxyphenyl)-2-methyl-3-(1-naphthyl)-2-(piperazin-1-ylcarbonyl)propanenitrile (377 mg, 0.913 mmol), meta-trifluoromethoxy bromobenzene (200 mg, 0.830 mmol), sodium tert-butoxide (111 mg, 1.16 mmol), tris(dibenzylideneacetone) dipalladium (0) (22.8 mg, 0.025 mmol), racemic BINAP (31 mg, 0.05 mmol), and toluene (3 mL) were combined in a Carius tube, vacuum degassed, placed under an argon atmosphere, sealed and heated to 80 C. overnight. The reaction was cooled, taken up in diethyl ether, filtered, washed with water, saturated aqueous sodium bicarbonate, brine, dried over MgSO4, filtered, evaporated, and purified on slica gel (10% hexanes/CH2Cl2) to yield 255 mg of the title compound as a white powder. 1H NMR 500 MHz (DMSO-D6): delta 7.97 (d, 1H, J=7.18 Hz), 7.88 (m, 1H), 7.84 (m, 1H), 7.78 (d, 1H, J=8.25 Hz), 7.52 (t, 1H, J=7.48 Hz), 7.41 (m, 2H), 7.30 (t, 1H, J=8.25 Hz), 7.23 (td, 1H, J=7.79 Hz, 1.68 Hz), 7.12 (m, 2H), 6.91 (dd, 1H, J=8.40 Hz, 1.68 Hz), 6.79 (m, 2H), 6.72 (d, 1H, J=8.09 Hz), 6.01 (s, 1H), 4.01 (s, 3H), 3.68 (bs, 4H0, 3.16 (bs, 4H) 1.63 (s, 3H) MS (ESI) m/z 574 ([M+H]+); Anal. calcd for C33H30F3N3O3. 0.35 C6H14: C, 69.82; H, 5.83; N, 6.96. Found: C, 69.81 H, 5.91; N, 6.74.

Reference： [1]Patent: US2005/256132,2005,A1

3
[ 52409-22-0 ]
[ 677298-01-0 ]
[ 78495-63-3 ]
[ 677298-04-3 ]

Yield	Reaction Conditions	Operation in experiment
17.5%	With potassium carbonate; triphenylphosphine; In ethanol; N,N-dimethyl acetamide; water;	[7-(2-Fluoro-6-methoxy-phenyl)-5-methyl-benzo[1,2,4]triazin-3-yl]-phenyl-amine To a solution of (7-Bromo-5-methyl-benzo[1,2,4]triazin-3-yl)-phenyl-amine (10 mg, 0.032 mmol) dissolved in 2 ml N,N-Dimethylacetamide in a 20 ml vial, 2-Fluoro-6-methoxy-phenylboronic acid (22 mg, 0.128 mmol) dissolved in 1 ml ethanol and potassium carbonate (6.4 mg, 0.06 mmol) dissolved in 1 ml water were added. Triphenylphosphine (1 mg, 0.0038 mmol) and tris(dibenzylideneacetone) dipalladium (0) (1 mg, 1.09 mmol) were added to the mixture. The mixture was reflux overnight. The crude product was filtered and purified by preparative HPLC. 2 mg [7-(2-Fluoro-6-methoxy-phenyl)-5-methyl-benzo[1,2,4]triazin-3-yl]-phenyl-amine was isolated. Yield: 17.5%; ESI-MS: [M+H]+, 361; 1H NMR (CDCl3): delta 2.73 (s, 3H), 3.83 (s, 3H), 6.83-6.86 (m, 2H), 7.14 (m, 1H), 7.34 (m, 1H), 7.45 (m, 2H), 7.75 (s, 1H), 7.92 (m, 2H), 8.24 (s, 1H).

Reference： [1]Patent: US2005/282814,2005,A1

4
[ 552331-08-5 ]
[ 52409-22-0 ]
[ 960-16-7 ]
[ 213697-53-1 ]
(1S)-{1-(1H-Indol-3-ylmethyl)-2-[5-(3-phenyl-isoquinolin-6-yl)-pyridin-3-yloxy]-ethyl}-carbamic Acid Tert-Butyl Ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
47%	With triethylamine; In ethyl acetate; N,N-dimethyl-formamide;	(1S)-{1-(1H-Indol-3-ylmethyl)-2-[5-(3-phenyl-isoquinolin-6-yl)-pyridin-3-yloxy]-ethyl}-carbamic Acid Tert-Butyl Ester To a solution of Example 80E (150 mg, 0.28 mmol), (1,1,1-tributylstannyl)benzene (137 mg, 0.57 mmol), tris(dibenzylideneacetone)-dipalladium (27 mg, 0.028 mmol) and 2-dicyclohexylphosphino-2'-dimethylamino-1,1'-biphenyl (22 mg, 0.057 mmol) in dry DMF (10 ml) triethyl amine was added under N2. The resulting solution was stirred 3 hours at 100 C. The reaction solution was partitioned between ethylacetate and water. The organic layer was washed (brine), dried (Na2SO4), filtered and concentrated under vacumm. Purification on silica gel with 60% ethyl acetate/hexane to provide the title compound (70 mg, 47%). MS (DCI/NH3) m/e 571 (M+1)+.

Reference： [1]Patent: US2003/187026,2003,A1

5
[ 13331-23-2 ]
[ 52409-22-0 ]
[ 5518-52-5 ]
[ 497-19-8 ]
[ 371970-08-0 ]
1-{3-[2-(4-Chlorophenyl)-5-(2-Furanyl)-1-Methyl-1H-Indol-3-yl]-1-Oxopropyl}-4-(Phenylmethyl)-4-Piperidinol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
30%	In 1,2-dimethoxyethane;	EXAMPLE 52 1-{3- [2-(4-Chlorophenyl)-5-(2-Furanyl)-1-Methyl-1H-Indol-3-yl]-1-Oxopropyl}-4-(Phenylmethyl)-4-Piperidinol 2-Furanylboronic acid (40 mg, 0.36 mmol) and aqueous sodium carbonate (2M, 1 mL) were added to a solution of 1-{3-[5-bromo-2-(4-chlorophenyl)-1-methyl-1H-indol-3-yl]-1-oxopropyl}-4-(phenylmethyl)-4-piperidinol (Example 49, 100 mg, 0.18 mmol) in 1,2-dimethoxyethane (10 mL) and the mixture was degassed. Tris(dibenzylideneacetone) dipalladium(0) (66 mg) and tris(2-furanyl)phosphine (2 mg) were added and the mixture was degassed, then heated to 75 C. overnight. The mixture was cooled and poured into aqueous sodium hydrogen carbonate (saturated, 50 mL) and extracted with ethyl acetate (4*25 mL). The combined organic fractions were washed with brine, dried (MgSO4) and the solvent was evaporated under reduced pressure. The residue was purified by medium pressure liquid chromatography on silica gel, eluding with ethyl acetate: isohexane (1:1), to give the title compound (30 mg, 30%). 1H NMR (360 MHz, CDCl3) delta7.95 (1H, d, J 1.7 Hz), 7.61 (1H, dd, J 1.6, 8.3 Hz), 7.49-7.47 (3H, m), 7.34-7.26 (6H, m), 7.12 (2H, dd, J 1.6, 8.3 Hz), 6.63 (1H, d, J 3.2 Hz), 4.34 (1H, br d, J 12.6 Hz), 3.57 (3H, s), 3.37 (1H, br d, J 10.5 Hz), 3.18 (1H, dt, Jt 11.3, Jd 1.5 Hz), 3.10-3.04 (2H, m), 2.90-2.82 (1H, m), 2.63 (2H, s), 2.58-2.52 (2H, m), 1.47-1.42 (2H, m), 1.34 (1H, br d, J 13.8 Hz), and 1.22-1.16 (1H, m). m/z (ES+) 553, 555 (M+1).

Reference： [1]Patent: US2001/39286,2001,A1

6
[ 110-91-8 ]
[ 52409-22-0 ]
trifluoromethanesulfonic acid 4-acetyl-3,5-dihydroxy-phenyl ester [ No CAS ]
[ 224311-51-7 ]
[ 404011-08-1 ]

Yield	Reaction Conditions	Operation in experiment
475 mg (60%)	With potassium phosphate; In tetrahydrofuran;	EXAMPLE 144 1-(2,6-Dihydroxy-4-morpholin-4-yl-phenyl)-ethanone A solution of trifluoromethanesulfonic acid 4-acetyl-3,5-dihydroxy-phenyl ester (1.0 g, 3.33 mmol), morpholine (0.35 mL, 3.99 mmol), tris-(dibenzylideneacetone)dipalladium(0) (153 mg, 0.167 mmol), <strong>[224311-51-7]biphenyl-2-yl-di-tert-butyl-phosphane</strong> (198 mg, 0.666 mmol), and K3PO4 (1.41 mg, 6.66 mmol) in THF (2 mL) was heated to 85° C. in a sealed tube for 2 h. The reaction mixture was allowed to cool to room temperature, and filtered through a 3/4" silica gel (60 A) plug. The plug was washed with EtOAc (75 mL) and the filtrate concentrated. The concentrate was purified via Biotage chromatography with gradient elution from 100percent hexanes to 40percent EtOAc/hexanes to yield 475 mg (60percent) of 1-(2,6-dihydroxy-4-morpholin-4-yl-phenyl)-ethanone. Rf=0.16 (50percent EtOAc/hexanes). 1H NMR (CDCl3, 400 MHz) delta7.26 (s, 2H), 5.82 (s, 2H), 3.79 (c, 4H), 3.26 (m, 4H), 2.65 (s, 3H). LRMS (Electrospray, positive): Da/e 238.3 (m+1).

Reference： [1]Patent: US2002/165218,2002,A1

7
[ 5308-25-8 ]
[ 53939-30-3 ]
[ 52409-22-0 ]
[ 213697-53-1 ]
1-(6-chloro-3-pyridinyl)-4-ethylpiperazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
269 mg (60%)	With sodium t-butanolate; In ethyl acetate; toluene;	REFERENCE EXAMPLE 85 1-(6-Chloro-3-pyridinyl)-4-ethylpiperazine A mixture of 5-bromo-2-chloropyridine (384 mg, 2.0 mmol), 1-ethylpiperazine (228 mg, 2.0 mmol), sodium tert-butoxide (576 mg, 6 mrnmol), tris(dibenzylideneacetone) dipalladium(0) (18.3 mg, 0.02 mmol), and 2-dicyclohexylphosphino-2'-(N,N-dimethylamino) biphenyl (23.6 mg, 0.06 mmol) in 10 mL of toluene was heated at reflux for 1 hour and concentrated. The residue was purified by flash column chromatography, eluding with 5% methanol in ethyl acetate to provide 269 mg (60%) of 1-(6-chloro-3-pyridinyl)-4-ethylpiperazine as a brown semi-solid: MS 225.9 (M+H) +.

Reference： [1]Patent: US2002/26052,2002,A1

8
[ 52409-22-0 ]
[ 108-86-1 ]
[ 177-11-7 ]
[ 865-48-5 ]
[ 19125-34-9 ]

Yield	Reaction Conditions	Operation in experiment
	In toluene;	(a) N-Phenyl-4-piperidone. 1,4-Dioxa-8-azaspiro[4.5]-decane (2.0 g, 14.0 mmol, 1.0 equiv), Pd2(DBA)3 (0.31 g, 0.34 mmol, 0.024 equiv), BINAP (0.64 g, 1.0 mmol, 0.073 equiv), NaO-t-Bu (3.9 g, 41 mmol, 3.0 equiv) and bromobenzene (2.6 g, 17.7 mmol, 1.3 equiv) were combined under Ar in 50 mL of dry toluene. The resulting mixture was refluxed under Ar for 4 h. The reaction mix was cooled and poured into 250 mL of saturated sodium bicarbonate solution. The product was extracted with 3*100 mL CH2Cl2.

Reference： [1]Patent: US2002/58809,2002,A1

9
[ 4318-42-7 ]
[ 52409-22-0 ]
[ 619-42-1 ]
[ 213697-53-1 ]
4-[4-Isopropyl-piperazin-1-yl]-benzoic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; In 1,2-dimethoxyethane; diethyl ether; water; pentane;	A. 4-[4-Isopropyl-piperazin-1-yl]-benzoic acid methyl ester Tris-(dibenzylidene-acetone)-dipalladium (0.05 mmol), (2'-dicyclohexylphosphanyl-biphenyl-2-yl)-dimethyl-amine (0.1 mmol) and potassium carbonate (4.6 mmol) are suspended in 1,2-dimethoxyethane (10 ml) in an oxygen-free atmosphere (N2). 4-Bromo-benzoic acid methyl ester (3.3 mmol) and 1-isopropyl-piperazine (3.9 mmol) are added and the stirred mixture is heated under reflux for 28 hours. After cooling the solvent is evaporated and water is added to the residue, which is then extracted three times with ethyl acetate. The combined extract is dried over sodium sulfate and evaporated. The residue is purified by flash chromatography on silica gel with (CH2Cl2/MeOH=95:5) as mobile phase. The product containing fractions are combined and evaporated. The residue is suspended in diethylether/pentane and the solid filtered of and dried (vacuum). A pale-brown powder with Rf=0.23 (CH2Cl2/MeOH=95:5) is obtained.

Reference： [1]Patent: US2001/16207,2001,A1

10
[ 52409-22-0 ]
[ 2759-28-6 ]
[ 619-42-1 ]
[ 213697-53-1 ]
4-(4-Benzyl-piperazin-1-yl)-benzoic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium t-butanolate; In diethyl ether; ethyl acetate; toluene;	A. 4-(4-Benzyl-piperazin-1-yl)-benzoic acid methyl ester Tris-(dibenzylidene-acetone)-dipalladium (0.03 mmol), (2'-dicyclohexylphosphanyl-biphenyl-2-yl)-dimethyl-amine (0.9 mmol) and NaOtBu (6.5 mmol) are suspended in toluene (20 ml) in an oxygen-free atmosphere (N2). 4-Bromo-benzoic acid methyl ester (4.65 mmol) and 1-(benzyl)-piperazine (5.6 mmol) are added and the stirred mixture is heated under reflux for 4 hours. After cooling, a mixture of ethylacetate and diethylether is added and the mixture is filtered. Then the solvent is evaporated and the residue is suspended in diethylether and the solid filtered of and dried (vacuum). A pale powder with mp. 105-107 C., Rf=0.67 (CH2Cl2/MeOH=95:5) is obtained.

Reference： [1]Patent: US2001/16207,2001,A1

11
[ 52409-22-0 ]
[ 402924-92-9 ]
[ 213697-53-1 ]
[ 402924-93-0 ]
4-benzyloxy-2-[7-(tert-butyl-dimethyl-silanyloxy)-naphthalen-1-ylamino]-benzoic acid benzyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With NaH; In toluene; mineral oil;	Example 54H 4-benzyloxy-2-[7-(tert-butyl-dimethyl-silanyloxy)-naphthalen-1-ylamino]-benzoic Acid Benzyl Ester A mixture of benzyl-2-bromo-4-benzyloxybenzoate (285 mg, 0.717 mmol), 2-(tertbutyldimethylsilyloxy)-8-aminonaphthalene (196 mg, 0.717 mmol), tris-(dibenzylideneacetone)dipalladium (4 mg, 0.004 mmol), (2'-dicyclohexylphosphanyl-biphenyl-2-yl)-dimethyl-amine (6 mg, 0.015 mmol) and 60% NaH in mineral oil (45 mg, 1.1 mmol) in toluene (3 mL) was heated to reflux under N2 for 1 hour, poured into water (10 mL) acidified to a pH <3with aqueous 1M HCl and extracted with diethyl ether (35 mL). The combined ether layers were washed with brine (15 mL), dried (MgSO4), filtered, concentrated under reduced pressure and purified silica gel eluding with 10% ethyl acetate/hexanes to provide the titled compound.

Reference： [1]Patent: US2002/35137,2002,A1

12
[ 52409-22-0 ]
[ 603-32-7 ]
[ 934-07-6 ]
[ 83629-92-9 ]
[ 368209-69-2 ]

Yield	Reaction Conditions	Operation in experiment
0.21 g (55%)		5-Bromo-1H-pyrrole-2-carboxylic acid methyl ester (1.49 mmol, 0.30 g, prepared according to the procedure described in Method 4 of Example 2) in NMP (10 ml) was treated with triphenylarsine (0.30 mmol, 91 mg), tris(dibenzylideneacetone) dipalladium(0) (0.07 mmol, 68 mg), and 4-(trimethylstannyl)-isoquinoline (2.22 mmol, 0.65 g), then heated to reflux under an argon atmosphere overnight. The resulting mixture was concentrated under reduced pressure, then purified by silica gel chromatography to provide 0.21 g (55%) of 5-isoquinolin-4-yl-1H-pyrrole-2-carboxylic acid methyl ester. 1H NMR (CDCl3) delta9.81 (1H, br s), 9.35 (1H, s), 8.66 (1H, s), 8.31 (1H, d, J=8.5), 8.10 (1H, d, J=8.1), 7.91 (1H, t, J=15.2), 7.79 (1H, t, J 15.2), 7.11 (1H, dd, J=3.8, 2.5), 6.64 (1H, dd, J=3.7, 2.7), 3.90 (3H, s).

Reference： [1]Patent: US2002/6943,2002,A1

13
potassium phosphate [ No CAS ]
[ 52409-22-0 ]
3-benzoyl-10-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4,5,6-hexahydroazepino[4,5-b]indole [ No CAS ]
Ar [ No CAS ]
[ 392-83-6 ]
3-benzoyl-10-[2-(trifluoromethyl)phenyl]-1,2,3,4,5,6-hexahydroazepino[4,5-b]indole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With phosphorous acid trimethyl ester;SiO2; In 1,4-dioxane; toluene;	Preparation 118 Preparation of 3-benzoyl-10-[2-(trifluoromethyl)phenyl]-1,2,3,4,5,6-hexahydroazepino[4,5-b]indole 3-Benzoyl-10-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4,5,6-hexahydroazepino[4,5-b]indole (2.50 g, 6.00 mmol), triturated potassium phosphate (3.01 g, 14.2 mmol) and tris(dibenzylideneacetone) dipalladium(0) (0.562 g, 0.613 mmol) were combined in dioxane (63 mL) at rt under N2. 2-Bromobenzotrifluoride (0.98 mL, 1.62 g, 7.21 mmol) and trimethylphosphite (0.22 mL, 0.231 g, 1.86 mmol) were added to the reaction mixture by syringe. Ar was bubbled through the reaction mixture for 20 min. The reaction mixture was heated to reflux for 22 h. The reaction mixture was concentrated and the residue was taken up in toluene (150 mL) and H2O (200 mL). The layers were separated and the aqueous layer was extracted with toluene (1100 mL, 150 mL). The combined organic layers were dried over MgSO4, filtered and concentrated. The crude product (3.90 g) was chromatographed (SiO2 250 g, eluted with 2:1 toluene:EtOAc) to yield 3-benzoyl-10-[2-(trifluoromethyl)phenyl]-1,2,3,4,5,6-hexahydroazepino[4,5-b]indole (2.48 g) in 95% yield. IR (diffuse reflectance) 3294, 1617, 1575, 1461, 1439, 1423, 1346, 1334, 1316, 1276, 1266, 1259, 1178, 1170, 1126, 1113, 1105, 1058, 1034, 792, 775, 755, 719, 701, 626 cm-1; MS (ESI+) for C26H21F3N2O m/z 435.0 (M+H)+; Anal. Calcd for C26H21F3N2O: C, 71.88; H, 4.87; N, 6.45; found: C, 71.94; H, 4.93; N, 6.48.

Reference： [1]Patent: US2002/77318,2002,A1

14
[ 52409-22-0 ]
[ 438210-30-1 ]
[ 161265-03-8 ]
2-(4-nitrophenyl)-6-(phenylamino)-2-hydroisoguinolin-1-one [ No CAS ]
[ 438210-21-0 ]

Yield	Reaction Conditions	Operation in experiment
81%	With caesium carbonate; aniline; In 1,4-dioxane; toluene;	A. 2-(4-nitrophenyl)-6-(phenylamino)-2-hydroisoguinolin-1-one To a dry RBF under argon was added 6-bromo-2-(4-nitrophenyl)-2-hydroisoquinolin-1-one (66 mg, 0.191 mmol) (prepared as outlined in Example 1125), cesium carbonate (106 mg, 0.325 mmol), tris(dibenzylideneacetone) dipalladium(0) (3.5 mg, 0.076 mmol), 9,9-dimethyl-4,5-bis(diphenylphosphino) xanthene (12 mg, 0.0207 mmol) and neat aniline (0.026 mL, 0.285 mmol). To this flask was added dry dioxane (0.5 mL) and dry toluene (0.5 mL). The reaction was stirred at 80 C. for 5 hr, concentrated and chromatographed on silica gel to give pure 2-(4-nitrophenyl)-6-(phenylamino)-2-hydroisoquinolin-1-one (55 mg, 81%). ES-MS (M+H)+=358.
81%	With caesium carbonate; aniline; In 1,4-dioxane; toluene;	A. 2-(4-nitrophenyl)-6-(phenylamino)-2-hydroisoguinolin-1-one To a dry RBF under argon was added 6-bromo-2-(4-nitrophenyl)-2-hydroisoquinolin-1-one (66 mg, 0.191 mmol) (prepared as outlined in Example 1125), cesium carbonate (106 mg, 0.325 mmol), tris(dibenzylideneacetone) dipalladium(0) (3.5 mg, 0.076 mmol), 9,9-dimethyl-4,5-bis(diphenylphosphino) xanthene (12 mg, 0.0207 mmol) and neat aniline (0.026 mL, 0.285 mmol). To this flask was added dry dioxane (0.5 mL) and dry toluene (0.5 mL). The reaction was stirred at 80 C. for 5 hr, concentrated and chromatographed on silica gel to give pure 2-(4-nitrophenyl)-6-(phenylamino)-2-hydroisoquinolin-1-one (55 mg, 81%). ES-MS (M+H)+=358.

Reference： [1]Patent: US2002/77486,2002,A1
[2]Patent: US6906063,2005,B2

15
[ 52409-22-0 ]
[ 22282-75-3 ]
[ 6163-58-2 ]
[ 203520-03-0 ]
[ 211820-04-1 ]

Yield	Reaction Conditions	Operation in experiment
	In 1,4-dioxane; dichloromethane;	To a suspension of <strong>[22282-75-3]3-fluoro-4-iodopyridine</strong> (2.23 g), 1-(tert-butoxycarbonyl)-4-(piperidin-4-ylcarbonyl)piperazine (1.49 g) and sodium t-butoxide (1.06 g) in 1,4-dioxan (20 ml) was added tris(dibenzylidene acetone)dipalladium(0) (0.09 g) and tri-o-tolylphosphine (0.12 g) and the mixture heated at reflux for 3 hours. The mixture was diluted with diethyl ether and washed with saturated aqueous sodium chloride solution, dried (Na2SO4) and evaporated. The residue was purified by chromatography on alumina (N32-63) eluding with 0.4percent methanol in dichloromethane to give as a solid, 1-(tert-butoxycarbonyl)-4-[1-(3-fluoro-4-pyridyl)piperidin-4-ylcarbonyl]piperazine (0.70 g). 1H-NMR (CDCl3): 1.45 (s, 9H), 1.80 (m, 2H), 2.00 (m, 2H), 2.65 (m, 1H), 2.90 (m, 2H), 3.40 (m, 8H), 3.80 (m, 2H), 6.70 (dd, 1H), 8.10 (d, 1H) and 8.20 (d, 1H); m/z 393 (M+1).
	In 1,4-dioxane; dichloromethane;	To a suspension of <strong>[22282-75-3]3-fluoro-4-iodopyridine</strong> (2.23 g), 1-(tert-butoxycarbonyl)-4-(piperidin-4-ylcarbonyl) piperazine (1.49 g) and sodium t-butoxide (1.06 g) in 1,4-dioxan (20 ml) was added tris(dibenzylidene acetone)dipalladium(0) (0.09 g) and tri-o-tolylphosphine (0.12 g) and the mixture heated at reflux for 3 hours. The mixture was diluted with diethyl ether and washed with saturated aqueous sodium chloride solution. dried (Na2SO4) and evaporated. The residue was purified by chromatography on alumina (N32-63) eluding with 0.4percent methanol in dichloromethane to give as a solid, 1-(tert-butoxycarbonyl)-4-[1-(3-fluoro-4-pyridyl)piperidin-4-ylcarbonyl]piperazine (0.70 g). 1H-NMR (CDCl3): 1.45 (s, 9H), 1.80 (m, 2H), 2.00 (m, 2H), 2.65 (m, 1H), 2.90 (m, 2H), 3.40 (m, 8H), 3.80 (m, 2H), 6.70 (dd, 1H), 8.10 (d, 1H) and 8.20 (d, 1H); m/z 393 (M+1).

Reference： [1]Patent: US6440972,2002,B1
[2]Patent: US6440972,2002,B1

16
[ 52409-22-0 ]
[ 628-17-1 ]
[ 5720-07-0 ]
[ 154607-00-8 ]
2-methoxy-7-pentoxyfluorenone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; sodium carbonate; potassium carbonate;aluminium trichloride; In 1,2-dimethoxyethane; thionyl chloride; ethanol; dichloromethane; N,N-dimethyl-formamide;	Example 3 2-methoxy-7-pentoxyfluorenone <strong>[154607-00-8]Methyl 2-bromo-5-hydroxybenzoate</strong> (9.30 g, 40.26 mmol), 4-methoxyphenylboronic acid (6.54 g, 43.00 mmol), and tris(dibenzylideneacetone) dipalladium (0) (0.30 g, 0.33 mmol) were added to dimethoxyethane (75 mL) and 2M sodium carbonate (75 mL). The reaction mixture was stirred at reflux for 16 h then cooled and decanted and the residue washed with ethyl acetate. The combined organic layers were dried (MgSO4) and the solvent removed by rotary evaporation to afford 9.45 g of the coupled product (36.64 mmol, 91% yield). The coupled product (1.06 g, 4.10 mmol) was alkylated by treating it with pentyl iodide (1.16 g, 5.85 mmol) and potassium carbonate (1.38 g, 10.00 mmol) in DMF at 75 C. for 16 h. The cooled reaction mixture was partitioned between ethyl acetate and water. The solvent was removed from the combined organic layers by rotary evaporation to give the alkylated product. The alkylated product was hydrolyzed with 1N sodium hydroxide (10 mL) in refluxing ethanol (50 mL) until the TLC indicated that the saponification was complete. The cooled reaction mixture was acidified with 1N hydrochloric acid and extracted with methylene chloride. The organic layers were dried (MgSO4) and concentrated by rotary evaporation to give the acid. The acid was dissolved and warmed in thionyl chloride (50 mL) at 65 C. for 30 min. The solution was cooled to ambient temperature and the thionyl chloride was removed by rotary evaporation. The residue was dissolved in methylene chloride (50 mL) and aluminum chloride (0.67 g, 5.00 mmol) added. The reaction was stirred at ambient temperature for 2 h then quenched by adding the reaction mixture to a beaker containing 100 mL 1N hydrochloric acid and ice. The methylene chloride layer was separated and the acidic layer was washed with methylene chloride. The combined organic layers were dried (MgSO4) and the solvent removed by rotary evaporation to give 1.05 g of 2-methoxy-7-pentoxyfluorenone (3.55 mmol, 87% yield) as a red solid. 1 H NMR (300Mhz, CDCl3) delta 7.28 (d, J=8.3 Hz, 2H), 7.14 (s, 2H), 6.93 (d, J=8.3 Hz, 2H), 3.96 (q, J=7.5 Hz, 2H), 3.82 (s, 3H), 1.80 (p, J=7.6 Hz, 2H), 1.42 (m, 4H), 0.93 (t, J=7.5 Hz, 3H).

Reference： [1]Patent: US5736578,1998,A

17
[ 110-91-8 ]
[ 52409-22-0 ]
[ 219571-41-2 ]
[ 1184-88-9 ]
[ 76144-87-1 ]
[ 280583-02-0 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; In methanol; chloroform; water; N,N-dimethyl-formamide; toluene;	Example 70 <Synthesis of 1-(2-chloro-4-morpholinobenzyl)-2-methyl-6-((4-methylbenzene)sulfonylcarbamoyl)benzimidazole (70)> 1-(4-bromo-2-chlorobenzyl)-2-methyl-6-((4-methylbenzene)sulfonylcarbamoyl)benzimidazole (250 mg) was dissolved in 3 ml of toluene, to which 63 mg of sodium t-butyrate, 49 mg of morpholine, 2.2 mg of (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and 1.1 mg of tris(dibenzylideneacetone) dipalladium (0) were added in this order in a nitrogen atmosphere, and the solution was stirred at100°C for 20 hours. The reaction solution was concentrated under reduced pressure, and water was added thereto. Hydrochloric acid (1 N) was added to the solution to adjust to a pH of 7, and the solution was extracted with a mixture of chloroform and methanol at a ratio of 4:1. The organic layer was washed with saturated brine, dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residue was subjected to silica-gel column chromatography and eluted with a mixture of chloroform and methanol at a ratio of 30:1. The desired fractions were concentrated under reduced pressure. The residue was dissolved in 3.0 ml of N,N-dimethylformamide, and 3.2 ml of water was gradually added thereto in an oil bath at 80°C. The solution was allowed to cool. The crystals precipitated were collected through filtration, and dried under reduced pressure while being heated to give 103 mg of the title compound as pale yellow crystals.

Reference： [1]Patent: EP1142880,2001,A1

18
potassium phosphate [ No CAS ]
[ 52409-22-0 ]
[ 700844-28-6 ]
[ 98446-49-2 ]
[ 213697-53-1 ]
[ 700844-86-6 ]

Yield	Reaction Conditions	Operation in experiment
	In 1,2-dimethoxyethane; hexane; ethyl acetate;	EXAMPLE 50 tert-Butyl (2E)-3-{6-cyano-7-[(2,4-dichloro-5-methoxyphenyl)amino]thieno[3,2-b]pyridin-2-yl}prop-2-enoate A mixture of tert-butyl (2E)-3-(7-chloro-6-cyanothieno[3,2-b]pyridin-2-yl)prop-2-enoate (1.29 g, 3.74 mmol), <strong>[98446-49-2]2,4-dichloro-5-methoxyaniline</strong> (862 mg, 4.49 mmol), Tris(dibenzylideneacetone)-dipalladium(0) (343 mg, 0.37 mmol), potassium phosphate (1.29 g, 5.61 mmol) and 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl (456 mg, 1.16 mmol) in 36 mL of ethylene glycol dimethyl ether is heated at 90 C. for 3 hours. The reaction mixture is cooled to room temperature and partitioned between water and ethyl acetate. The aqueous layer is extracted with additional ethyl acetate and the organic layers are combined, dried over sodium sulfate, filtered and concentrated in vacuo. The residue is purified by flash column chromatography eluding with a gradient of hexane to 40% ethyl acetate in hexane to provide 974 mg of tert-butyl (2E)-3-{6-cyano-7-[(2,4-dichloro-5-methoxyphenyl)amino]thieno[3,2-b]pyridin-2-yl}prop-2-enoate as a light tan solid, mp 224 C. dec; 1H NMR (DMSO-d6) delta 1.48 (s, 9H), 3.85 (s, 3H), 6.26 (d, J=16 Hz, 1H), 7.37 (s, 1H), 7.75 (d, J=16 Hz, 1H), 7.78 (s, 1H), 7.91 (s, 1H), 8.62 (s, 1H), 9.80 (s, 1H); MS 476.0, 478.0 (M+H)+. Analysis for C22H19Cl2N3O3S-0.4 H2O: Calcd: C, 54.64; H, 4.13; N, 8.69. Found: C, 54.51; H, 3.96; N, 8.50.

Reference： [1]Patent: US2004/242883,2004,A1

19
[ 52409-22-0 ]
aqueous potassium fluoride [ No CAS ]
[ 745078-70-0 ]
[ 5518-52-5 ]
[ 745078-71-1 ]

Yield	Reaction Conditions	Operation in experiment
	With tri-n-butyl-tin hydride; In ethyl acetate; N,N-dimethyl-formamide;	Example 1D ethyl 5-(3-((1E)-3-hydroxyprop-1-enyl)phenyl)isoxazole-3-carboxylate The tributyltin reagent from Example 1C (665 muL, 1.83 mmol) was added under nitrogen atmosphere to a mixture of alcohol from Example 1B (433 mg, 1.66 mmol), tris(dibenzylideneacetone)-dipalladium(0) (76 mg, 0.083 mmol), <strong>[5518-52-5]tri-2-furylphosphine</strong> (39 mg, 0.166 mmol), and cupper(I) iodide (32 mg, 0.166 mmol) in DMF (7 mL). The reaction mixture was stirred at ambient temperature for 30 minutes. Aqueous potassium fluoride was added to the mixture and the resulting suspension was filtered through celite and washed with ethyl acetate. The filtrate was taken up in ethyl acetate and water. The organic phase was washed with brine (*3), dried (MgSO4), filtered and concentrated under reduced pressure and purified by flash chromatography on silica gel with hexane/ethyl acetate (1:1) to provide the titled compound (353 mg). MS (ESI(+)) m/e 291 (M+18)+; 1H NMR (500 MHz, DMSO-d6) delta 8.05(t, J=1.7 Hz, 1H), 7.80 (dt, J1=1.7 Hz, J2=7.5 Hz, 1H), 7.60 (dt, J1=1.7 Hz, J2=7.5 Hz, 1H), 7.57 (s, 1H), 7.51(t, J=7.5 Hz, 1H), 6.63-6.59 (m, 2H), 4.94 (t, J=5.4 Hz, 1H), 4.41 (q, J=7.1 Hz, 2H), 4.19-4.14(m, 2H), 1.35 (t, J=7.1 Hz, 3H).

Reference： [1]Patent: US2004/167188,2004,A1

20
[ 52409-22-0 ]
[ 369-35-7 ]
[ 55052-28-3 ]
[ 564483-18-7 ]
[ 869335-25-1 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; In ethyl acetate; tert-butyl alcohol;	Example 8A N-(2-Fluoro-4-nitrophenyl)-1H-pyrrolo[2,3-b]pyridine-4-amine A solution of 500 mg (3.28 mmol) of 4-chloro-1H-pyrrolo[2,3-b]pyridine (Schneller, Stewart, W.; Luo, Jiann-Kuan; J. Org. Chem. 1980, 45, 4045-4048.), 614 mg (3.93 mmol) of <strong>[369-35-7]2-fluoro-4-nitroaniline</strong>, 150 mg (0.16 mmol) of tris(dibenzylidenacetone)dipalladium and 156 mg (0.33 mmol) of dicyclohexyl(2',4',6'-triisopropylbiphenyl-2-yl)phosphine and 996 mg (7.21 mmol) of potassium carbonate in 5.00 ml of degassed tert-butanol is stirred in a sealed pressure vessel at 100 C. for 3 h. After cooling to RT, the mixture is filtered through Celite, the Celite is washed with ethyl acetate and the filtrates are concentrated under reduced pressure. The residue is purified by column chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate 1:1). Yield: 694 mg (78% of theory)

Reference： [1]Patent: US2008/269268,2008,A1

21
[ 52409-22-0 ]
dppf [ No CAS ]
[ 869335-39-7 ]
[ 2996-30-7 ]
[ 869335-40-0 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium t-butanolate; In ethyl acetate; toluene;	Example 27A N-(2-Fluoro-4-nitrophenyl)-3-methyl-1-[2-(trimethylsilyl)ethoxy]methyl}-1H-pyrrolo[2,3-b]pyridine-4-amine A solution of 29 mg (100 mumol) of 3-methyl-1-[2-(trimethylsilyl)ethoxy]methyl}-1H-pyrrolo[2,3-b]pyridine-4-amine, 33 mg (130 mumol) of <strong>[2996-30-7]2-fluoro-1-iodo-4-nitrobenzene</strong>, 5 mg (10 mumol) of tris-(dibenzylideneacetone)dipalladium, 6 mg (10 mmol) of 1,1'-bis(diphenylphosphino)ferrocene and 14 mg (150 mmol) of sodium tert-butoxide in 3 ml of degassed toluene is stirred at 100 C. overnight. After cooling to RT, the reaction mixture is directly applied to a silica gel column and separated (mobile phase: cyclohexane/ethyl acetate 10:1 to 8:2). Yield: 20 mg (46% of theory) LC-MS (Method 9): Rt=2.78 min. MS (ESI pos.): m/z=417 (M+H)+.

Reference： [1]Patent: US2008/269268,2008,A1

22
[ 52409-22-0 ]
dppf [ No CAS ]
[ 869335-48-8 ]
[ 2996-30-7 ]
[ 869335-49-9 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium t-butanolate; In ethyl acetate; toluene;	Example 36A N-(2-Fluoro-4-nitrophenyl)-<strong>[869335-48-8]1-methyl-1H-pyrrolo[2,3-b]pyridine-4-amine</strong> A solution of 260 mg (1.77 mmol) of <strong>[869335-48-8]1-methyl-1H-pyrrolo[2,3-b]pyridine-4-amine</strong>, 566 mg (2.12 mmol) of 2-fluoro-1-iodo-4-nitrobenzene, 81 mg (0.09 mmol) of tris(dibenzylidene-acetone)dipalladium, 98 mg (0.18 mmol) of 1,1'-bis(diphenylphosphino)ferrocene and 238 mg (2.47 mmol) of sodium tert-butoxide in 8 ml of degassed toluene is stirred at 100° C. overnight. After cooling to RT, the reaction mixture is applied directly to a silica gel column and separated (mobile phase: cyclohexane/ethyl acetate 10:1 to 1:1). Yield: 210 mg (42percent of theory) LC-MS (Method 8): Rt=1.89 min. MS (ESI pos.): m/z=287 (M+H)+. 1H-NMR (DMSO-d6, 300 MHz): delta=3.80 (s, 3H), 6.48 (d, 1H), 6.83 (d, 1H), 7.35 (dd, 1H), 7.40 (d, 1H), 8.03 (d, 1H), 8.13 (d, 1H), 8.18 (d, 1H), 9.32 (s, 1H).

Reference： [1]Patent: US2008/269268,2008,A1

23
[ 657408-07-6 ]
[ 52409-22-0 ]
potassium phosphate monohydrate [ No CAS ]
[ 84110-40-7 ]
[ 1272455-58-9 ]
[ 1272455-72-7 ]

Yield	Reaction Conditions	Operation in experiment
	In dichloromethane; water; ethyl acetate; toluene;	Example 5 Synthesis of Compound 5 Synthesis of N-(3,5-diisobutylbiphenyl-4-yl)benzamide. A mixture of N-(3,5-dibromobiphenyl-4-yl)benzamide (8.52 g, 19.8 mmol), isobutyl boronic acid (8.06 g, 79.2 mmol), potassium phosphate monohydrate (13.7 g, 59.4 mmol), water. (50 mL) and toluene (150 mL) was purged with nitrogen for 20 min before addition of tris(dibenzylideneacetone) dipalladium(0) (0.27 g 3% Pd) and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.49 g, 6 mol %). The reaction was stirred at reflux for 18 h. After cooling to ambient temperature the mixture was diluted with ethyl acetate and water. The layers were separated and the organic layer was concentrated and chromatographed on a silica gel column. Elution first with dichloromethane then dichloromethane and ethyl acetate (49:1) gave 6.53 g (86% yield) of the desired product as a solid. 1H NMR confirmed the structure. Synthesis of 1-(3,5-diisobutylbiphenyl-4-yl)-2-phenyl-1H-imidazole.

Reference： [1]Patent: US2011/57559,2011,A1

24
[ 52409-22-0 ]
[ 932710-63-9 ]
[ 1356682-55-7 ]
[ 145214-05-7 ]
[ 1356681-60-1 ]

Yield	Reaction Conditions	Operation in experiment
735 mg (0.888 mmol, 88%)	In tetrahydrofuran; hexane; ethyl acetate;	Step A 9-{5-O-[bis(4-methoxyphenyl)(phenyl)methyl]-2-o-[4-(1,3-oxazol-2-yl)benzyl]-beta-D-ribofuranosyl}-6-[2-(trimethylsilyl)ethoxy]-9H-purine Tris[dibenzylideneacetone]dipalladium(0) (131 mg, 0.143 mmol) and <strong>[932710-63-9][4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine</strong> (152 mg, 0.572 mmol) were added to THF (10 mL) at ambient temperature and stirred for 30 min. To this mixture was then added a solution of 9-{5-O-[bis(4-methoxyphenyl)(phenyl)methyl]-2-o-(4-bromobenzyl)-beta-D-ribofuranosyl}-6-[2-(trimethylsilyl)ethoxy]-9H-purine (Intermediate 3, 800 mg, 0.953 mmol) and 2-(tri-N-butylstannyl)oxazole (1.02 g, 2.86 mmol) in THF (15 mL). The mixture was heated at 50 C. and stirred for 16 h. After cooled to ambient temperature, the mixture was filtered through a layer of Celite. The filtrate was concentrated in vacuo. The residue was purified with flash chromatography using 55-60% ethyl acetate in hexane to obtain 735 mg (0.888 mmol, 88%) of the pure product. LCMS: for C46H49N5O8Si calculated 828.0. found 828.3 [M+H]+. 1H NMR (600 MHz, CD3CN) delta: 8.22 (s, 1H), 8.05 (s, 1H), 7.88 (s, 1H), 7.77 (d, J=8.2 Hz, 2H), 7.41 (d, J=8.0 Hz, 2H), 7.25 (m, 7H), 6.80 (m, 4H), 6.09, (d, J=5.5 Hz, 1H), 4.78 (m, 2H), 4.58 (m, 4H), 4.19 (dd, J=8.4, 4.3 Hz, 1H), 3.76 (s, 6H), 3.59 (d, J=5.2 Hz, 2H), 3.33 (d, J=4.5 Hz, 2H), 1.21 (m, 2H), 0.10 (s, 9H). 13C NMR (600 MHz, CD3CN) delta: 158.82, 151.74, 145.21, 141.78, 140.29, 139.61, 136.05, 136.00, 130.21, 130.17, 128.58, 128.40, 128.18, 127.98, 127.00, 126.00, 117.54, 117.07, 113.19, 87.14, 86.34, 84.55, 80.02, 71.85, 69.98, 65.20, 63.53, 55.08, 17.18, -2.13.

Reference： [1]Patent: US2012/252027,2012,A1

25
[ 52409-22-0 ]
[ 6163-58-2 ]
[ 69861-71-8 ]

Reference： [1]Organometallics,2013,vol. 32,p. 3570 - 3573

26
[ 52409-22-0 ]
[ 2100-17-6 ]
[ 15022-08-9 ]
[ 3994-50-1 ]
[ 1586042-62-7 ]

Yield	Reaction Conditions	Operation in experiment
	With ammonium chloride; triphenylphosphine; In tetrahydrofuran; 1,4-dioxane; ethyl acetate;	Intermediate 8 5-(1-Allyloxypent-4-enyl)-<strong>[3994-50-1]1-methyl-4-nitro-pyrazole</strong> To a solution of <strong>[3994-50-1]1-methyl-4-nitro-pyrazole</strong> (9.7 g, 76.7 mmol) and pent-4-enal (10.0 g, 84.4 mmol) in THF (250 mL) at -78 C. was added dropwise a solution of LiHMDS in THF (1 M, 192 mL, 191.7 mmol). The reaction mixture was allowed to warm to -40 C. and stirred for 4 hr. The reaction was quenched with a saturated solution of ammonium chloride (100 mL), warmed to room temperature and the solvents removed under reduced pressure. The residue was dissolved in EtOAc (100 mL) and washed with water (30 mL). The organic layer was separated, dried over MgSO4 and concentrated under reduced pressure. Purification via silica gel column chromatography (0-30% EtOAc/isohexane) gave a clear oil. This oil (7.1 g, 33.6 mmol), diallyl carbonate (14.33 g, 100.9 mmol) and triphenylphosphine (880 mg, 3.35 mmol) were dissolved in dioxane (236 mL) under nitrogen before tris(dibenzylideneacetone)-dipalladium(0) (780 mg, 0.84 mmol) was added. The reaction mixture was heated at 50 C. for 1 hr and the solvent removed under reduced pressure. Purification via silica gel column chromatography (0-40% EtOAc/isohexane) gave 5-(1-allyloxypent-4-enyl)-<strong>[3994-50-1]1-methyl-4-nitro-pyrazole</strong> as a yellow oil (8.35 g, 43% over two steps). 1H NMR (400 MHz, CDCl3) delta 8.06 (s, 1H), 5.90-5.73 (m, 2H), 5.46 (dd, J=8.8, 5.1 Hz, 1H), 5.29-5.16 (m, 2H), 5.10-5.00 (m, 2H), 4.04 (s, 3H), 3.92 (d, J=5.8 Hz, 2H), 2.37-2.25 (m, 1H), 2.22-2.09 (m, 1H), 2.09-1.96 (m, 1H), 1.84 (dddd, J=13.7, 9.2, 6.9, 5.1 Hz, 1H).

Reference： [1]Patent: US2014/88117,2014,A1 .Location in patent: Page/Page column

27
[ 557-21-1 ]
[ 52409-22-0 ]
[ 65550-77-8 ]
[ 156072-84-3 ]

Yield	Reaction Conditions	Operation in experiment
76%		Step 1: Synthesis of 5-chloro-3-methylpicolinonitrile A mixture of <strong>[65550-77-8]2-bromo-5-chloro-3-methylpyridine</strong> (45 g, 218 mmol), zinc cyanide (8.30 mL, 131 mmol), tris(dibenzylideneacetone)dipalladium (0) (4.99 g, 5.45 mmol), and 1,1'-bis(diphenylphosphino)ferrocene (6.04 g, 10.90 mmol) in dimethylacetamide (40 mL) was heated to 110 C. for 4 hours. The reaction mixture was cooled to RT, diluted with water and extracted with ethyl acetate. The organic phase obtained was concentrated under reduced pressure and residue purified by chromatography on silica gel using ISCO eluting with 0-60% EtOAc/hex to afford the title compound 5-chloro-3-methylpicolinonitrile (25.4 g, 166 mmol, 76% yield). LC/MS (ESI+) m/z=153.1 (M+H).

Reference： [1]Patent: US2014/249104,2014,A1 .Location in patent: Page/Page column

28
[ 52409-22-0 ]
[ 1155270-72-6 ]
[ 73183-34-3 ]
[ 321921-71-5 ]
[ 1154741-25-9 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium acetate; In diethyl ether; water; acetonitrile;	Step 1: Preparation of intermediate (2,3-dihydropyrano[4,3,2-de]quinolin-7-yl)-boronic acid (3a) A vial containing the 7-bromo-2,3-dihydro-1-oxa-6-aza-phenalene (600 mg, 2.40 mmol, prepared according to ), tris(dibenzylidene acetone)dipalladium(0) (22 mg, 0.024 mmol), di(1-adamantyl)-n-butylphosphine (25.8 mg, 0.072 mmol), bis[pinacolato]diboron (731 mg, 2.88 mmol) and potassium acetate (706 mg, 7.20 mmol) was purged with argon for 10 minutes and then degassed anhydrous dimethylacetamide (2 mL) was added. The resulting mixture was stirred at 90C for 4 hours. The mixture was cooled to room temperature and water was added slowly (40 mL). The precipitate was filtered, washed with water (20 mL) and toluene (10 mL), dried in vacuo and triturated in diethyl ether. The powder was dissolved in acetonitrile and the solution was then filtered on Millipore and the filtrate concentrated in vacuo to provide (2,3-dihydropyrano[4,3,2-de]quinolin-7-yl)-boronic acid (3a) (301 mg, 1.39 mmol, 58%). 1H NMR (400 MHz, DMSO-d6 + D2O) d 3.27 (t, 2H, J = 5.8 Hz), 4.44 (t, 2H, J = 5.8 Hz), 7.03 (d, J = 7.8 Hz, 1 H), 7.35 (d, J = 4.5 Hz, 1 H), 8.16 (d, J = 7.8 Hz, 1 H), 8.83 (d, J = 4.5 Hz, 1 H).

Reference： [1]Patent: EP2821104,2015,A1 .Location in patent: Page/Page column

29
[ 52409-22-0 ]
[ 13716-12-6 ]
[ 53199-31-8 ]

Reference： [1]Organic Syntheses,2005,vol. 81,p. 63 - 76
[2]Angewandte Chemie - International Edition,2015,vol. 54,p. 10322 - 10326
Angew. Chem.,2015,vol. 127,p. 10462 - 10466,5

30
[ 52409-22-0 ]
[ 13375-29-6 ]
C₁₃H₁₇N [ No CAS ]

Reference： [1]Patent: US2017/27172,2017,A1 .Location in patent: Page/Page column 44

31
[ 52409-22-0 ]
[ 131274-22-1 ]
[ 53199-31-8 ]

Reference： [1]Journal of Organic Chemistry,2017,vol. 82,p. 5046 - 5067

32
[ 657408-07-6 ]
potassium phosphate [ No CAS ]
[ 52409-22-0 ]
(4-(10-bromoanthracen-9-yl)phenyl)diphenylphosphine oxide [ No CAS ]
[ 100622-34-2 ]
[ 96042-30-7 ]
(4-[9,9'-bianthracen-10-yl]phenyl)diphenylphosphine oxide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		3rd step: (4-[9,9'-bianthracen-10-yl]phenyl)diphenylphosphine oxide (4-(10-bromoanthracen-9-yl)phenyl)diphenyl phosphine oxide (5.0 g, 9.4 mmol, 1.0 eq), 9-anthracene boronic acid (3.12 g, 14.1 mmol, 1.5 eq), tris(dibenzylidenaceton)dipalladium(0) (172 mg, 0.19 mmol, 4.0 mol. %), dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine (308 mg, 0.75 mmol, 8.0 mol. %) and potassium phosphate (5.97 g, 28.1 mmol, 3.0 eq), were placed in a flask and suspended in toluene (20 mL). The resulting mixture was heated at 120 C. for 48 h. After cooling to RT, DCM and water were added; the organic phase was decanted and extracted with water until the aqueous was neutral. The aqueous layers were also extracted with ethyl acetate (2*200 mL) and decanted. The combined organic layers were extracted with an aqueous sodium diethylcarbamodithioate solution, decanted, dried over MgSO4, and evaporated to dryness. The crude product was then re-crystallized from 1,4-dioxane, and finally sublimed under reduced pressure. HPLC purity: 99.18% 1H NMR (CDCl3, 25 C.): delta=8.75 (s, 1H); 8.20 (d, J=8.6 Hz, 2H); 7.97 (dd, J=8.0, 11.7 Hz, 2H); 7.87 (m, 4H); 7.77 (m, 4H); 7.65 (m, 2H); 7.59 (m, 4H); 7.48 (m, 2H); 7.35 (m, 2H); 7.16 (m, 8H) ppm. 13C NMR (CDCl3, 25 C.): delta=143.62; 143.60; 137.12; 134.33; 134.05; 133.49; 133.22; 132.67; 132.56; 132.21; 131.77; 130.43; 129.27; 129.17; 127.98; 127.46; 127.41; 127.13; 126.51; 126.20; 126.14; 125.97 ppm

Reference： [1]Patent: US2018/114914,2018,A1

33
[ 52409-22-0 ]
[ 1070663-78-3 ]
N-benzyl-2-fluoro-N-(propa-1,2-dien-1-yl)benzenesulfonamide [ No CAS ]
C₅₁H₆₇FNO₄PPdS [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2018,vol. 57,p. 9930 - 9935
Angew. Chem.,2018,vol. 130,p. 10078 - 10083,6

34
[ 52409-22-0 ]
[ 4731-65-1 ]
N-benzyl-2-fluoro-N-(propa-1,2-dien-1-yl)benzenesulfonamide [ No CAS ]
C₃₇H₃₅FNO₅PPdS [ No CAS ]
C₅₈H₅₆FNO₈P₂PdS [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2018,vol. 57,p. 9930 - 9935
Angew. Chem.,2018,vol. 130,p. 10078 - 10083,6

35
[ 52409-22-0 ]
[ 658-27-5 ]
C₂₃H₁₉FN₂ [ No CAS ]

Reference： [1]RSC Advances,2018,vol. 8,p. 26523 - 26527

36
[ 52409-22-0 ]
[ 3107-34-4 ]
C₂₄H₁₇F₃N₂ [ No CAS ]

Reference： [1]RSC Advances,2018,vol. 8,p. 26523 - 26527

37
[ 52409-22-0 ]
[ 2924-16-5 ]
C₂₃H₁₇FN₂ [ No CAS ]

Reference： [1]RSC Advances,2018,vol. 8,p. 26523 - 26527

38
5-(di-tert-butylphosphino)-1′, 3′, 5′-triphenyl-1′H-[1,4′]bipyrazole [ No CAS ]
[ 52409-22-0 ]
[ 5744-80-9 ]
C₃₇H₄₂BrN₆PPd [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2019,vol. 84,p. 4653 - 4660

39
[ 866081-62-1 ]
[ 52409-22-0 ]
[ 591-50-4 ]
C₂₄H₃₃IN₂P₂Pd [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2020,vol. 59,p. 2105 - 2109
Angew. Chem.,2020,vol. 132,p. 2121 - 2125,5

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CAS No. :	52409-22-0	MDL No. :	MFCD00013310
Formula :	C₅₁H₄₂O₃Pd₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	-
M.W :	915.72	Pubchem ID :	-
Synonyms :

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P280	UN#:	N/A
Hazard Statements:	H302-H312-H332	Packing Group:	N/A
GHS Pictogram:

Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
P102	Keep out of reach of children.
P103	Read label before use
Prevention
Code	Phrase
P201	Obtain special instructions before use.
P202	Do not handle until all safety precautions have been read and understood.
P210	Keep away from heat/sparks/open flames/hot surfaces. - No smoking.
P211	Do not spray on an open flame or other ignition source.
P220	Keep/Store away from clothing/combustible materials.
P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

Physical hazards
Code	Phrase
H200	Unstable explosive
H201	Explosive; mass explosion hazard
H202	Explosive; severe projection hazard
H203	Explosive; fire, blast or projection hazard
H204	Fire or projection hazard
H205	May mass explode in fire
H220	Extremely flammable gas
H221	Flammable gas
H222	Extremely flammable aerosol
H223	Flammable aerosol
H224	Extremely flammable liquid and vapour
H225	Highly flammable liquid and vapour
H226	Flammable liquid and vapour
H227	Combustible liquid
H228	Flammable solid
H229	Pressurized container: may burst if heated
H230	May react explosively even in the absence of air
H231	May react explosively even in the absence of air at elevated pressure and/or temperature
H240	Heating may cause an explosion
H241	Heating may cause a fire or explosion
H242	Heating may cause a fire
H250	Catches fire spontaneously if exposed to air
H251	Self-heating; may catch fire
H252	Self-heating in large quantities; may catch fire
H260	In contact with water releases flammable gases which may ignite spontaneously
H261	In contact with water releases flammable gas
H270	May cause or intensify fire; oxidizer
H271	May cause fire or explosion; strong oxidizer
H272	May intensify fire; oxidizer
H280	Contains gas under pressure; may explode if heated
H281	Contains refrigerated gas; may cause cryogenic burns or injury
H290	May be corrosive to metals
Health hazards
Code	Phrase
H300	Fatal if swallowed
H301	Toxic if swallowed
H302	Harmful if swallowed
H303	May be harmful if swallowed
H304	May be fatal if swallowed and enters airways
H305	May be harmful if swallowed and enters airways
H310	Fatal in contact with skin
H311	Toxic in contact with skin
H312	Harmful in contact with skin
H313	May be harmful in contact with skin
H314	Causes severe skin burns and eye damage
H315	Causes skin irritation
H316	Causes mild skin irritation
H317	May cause an allergic skin reaction
H318	Causes serious eye damage
H319	Causes serious eye irritation
H320	Causes eye irritation
H330	Fatal if inhaled
H331	Toxic if inhaled
H332	Harmful if inhaled
H333	May be harmful if inhaled
H334	May cause allergy or asthma symptoms or breathing difficulties if inhaled
H335	May cause respiratory irritation
H336	May cause drowsiness or dizziness
H340	May cause genetic defects
H341	Suspected of causing genetic defects
H350	May cause cancer
H351	Suspected of causing cancer
H360	May damage fertility or the unborn child
H361	Suspected of damaging fertility or the unborn child
H361d	Suspected of damaging the unborn child
H362	May cause harm to breast-fed children
H370	Causes damage to organs
H371	May cause damage to organs
H372	Causes damage to organs through prolonged or repeated exposure
H373	May cause damage to organs through prolonged or repeated exposure
Environmental hazards
Code	Phrase
H400	Very toxic to aquatic life
H401	Toxic to aquatic life
H402	Harmful to aquatic life
H410	Very toxic to aquatic life with long-lasting effects
H411	Toxic to aquatic life with long-lasting effects
H412	Harmful to aquatic life with long-lasting effects
H413	May cause long-lasting harmful effects to aquatic life
H420	Harms public health and the environment by destroying ozone in the upper atmosphere

[ CAS No. 52409-22-0 ] {[proInfo.proName]}

Quality Control of [ 52409-22-0 ]

Related Doc. of [ 52409-22-0 ]

Product Details of [ 52409-22-0 ]

Safety of [ 52409-22-0 ]

Application In Synthesis of [ 52409-22-0 ]

[ 52409-22-0 ] Synthesis Path-Upstream 1~3

[ 52409-22-0 ] Synthesis Path-Downstream 1~39

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry