Name: 4334-87-6|3-Ethoxycarbonylphenylboronic acid|98%
Brand: Ambeed
SKU: A141248
Price: 5.0 USD
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1
[ 684284-68-2 ]
[ 4334-87-6 ]
[ 907201-03-0 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 120℃; for 3h;	To a solution of trifluoro-methanesulfonic acid 9-benzhydryloxy-7-(4-fluoro-benzyl)-8-oxo-7,8-dihydro-6H-pyrrolo[3,4-g]quinolin-5-yl ester 46 (43 mg, 0.07 mmol) dissolved in toluene (3 mL) /ethanol (0.6 mL) /water (0.4 mL) was added K2CO3 (29 mg, 0.21 mmol), (3-ethoxycarbonylphenyl) boronic acid (28 mg, 0.14 mmol) and tetrakis-(triphenylphosphine)-palladium(0) (16mg, 0.014 mmol). the reaction mixture in the flask was flashed with argon three times. It was then heated to 120C under argon 3 hours. The reaction was monitored by TLC (EtOAc/hexane 3/7) (Rf46 = 0.6, Rf277 = 0.3) and LC/MS. After cooling to room temperature, the mixture was diluted with EtOAc (20mL) and washed with 1N HCl, saturated NaHCO3 and brine. The organic phase was dried (MgSO4), filtered and concentrated in vacuo to afford crude 3-[9-benzhydryloxy-7-(4-fluoro-benzyl)-8-oxo-7,8-dihydro-6H-pyrrolo[3,4-g]quinolin-5-yl]-benzoic acid ethyl ester 277.
	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 120℃; for 6h;	To a solution of trifluoro-methanesulfonic acid 9-benzhydryloxy-7-(4-fluoro- benzyl)-8-oxo-7,8-dihydro-6H-pyrrolo[3,4-g]quinolin-5-yl ester 46 (43 mg, 0.07 mmol) dissolved in toluene (3 mL)/ ethanol (0.6 mL)/ water (0.4 mL) was added K2C03 (29 mg, 0.21 mmol), (3-ethoxycarbonylphenyl) boronic acid (28 mg, 0.14 mmol) and tetrakis-(triphenylphosphine)-palladium(0) (16 mg, 0.014mmol). The reaction mixture in the flask was flashed with argon three times. It was then heated to 120C under argon 3 hours. The reaction was monitored by TLC (EtOAc/hexane 3/7) (Rf46 = 0.6, Rf277 = 0.3) and LC/MS. After cooling to room temperature, the mixture was diluted with EtOAc (20mL) and washed with 1N HCl, saturated NaHC03 and brine. The organic phase was dried (MgS04), filtered and concentrated in vacuo to afford crude 3-[9-benzhydryloxy-7-(4-fluoro-benzyl)-8-oxo-7,8-dihydro- 6H-pyrrolo[3,4-g]quinolin-5-yl]-benzoic acid ethyl ester 277.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2006,vol. 16,p. 3989 - 3992
[2]Patent: WO2004/35576,2004,A2 .Location in patent: Page 316;317
[3]Patent: WO2005/117904,2005,A2 .Location in patent: Page/Page column 555-556

2
C₁₆H₂₂BrN₅O₂ [ No CAS ]
[ 4334-87-6 ]
C₂₅H₃₁N₅O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,2-dimethoxyethane; water; at 80℃;	Part G:; To a 25 ml round bottom flask charged with crude compound 8 (360 mg, 0.9 mmol), boronic acid (390 mg, 2.0 mmol), and PdCI2(dppf) (82 mg, 0.1 mmol) was added a DME (4 mL) and Na2CO3 (1 mL, sat. aq) . The mixture was thoroughly degassed by alternately connected the flask to vacuum and Argon. This resulting mixture was then heated at 80 0C overnight, diluted by EtOAc (40 ml) and washed with brine. After concentration, the residue was purified with column (silica gel, EtOAc to EtOAc/MeOH = 95/5) to give the product 9 (312 mg) as oil. HPLC-MS tR = 1.64 min (UV25* nm); mass calculated for formula C25H31N5O4465.2, observed LCMS m/z 466.3 (M+H).

Reference： [1]Patent: WO2007/145921,2007,A1 .Location in patent: Page/Page column 67

3
[ 863249-46-1 ]
[ 4334-87-6 ]
[ 1016979-22-8 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate;bis-triphenylphosphine-palladium(II) chloride; In ethanol; toluene; at 100℃; for 18h;	Step B; A mixture of 1-benzyl-3-methyl-1,2,3,6-tetrahydropyridin-4-yl trifluoromethanesulfonate (3 g, 9.0 mmol), <strong>[4334-87-6][3-(ethoxycarbonyl)phenyl]boronic acid</strong> (2.26 g, 11.6 mmol), PdCl2(PPh3)2 (315 mg, 0.44 mmol), and potassium carbonate (2.5 g, 18.0 mmol) in Toluene:EtOH (10:1, 50 mL) were heated to 100 C. for 18 hr. The cooled reaction mixture was partitioned between EtOAC and H2O and the aqueous layer was extrated with EtOAc (4×). The organics were combined, dried over sodium sulfate, filtered and evaporated to dryness. The residue was purified by column chromatography on silica gel eluting with a gradient of hexane:EtOAc to yield ethyl 3-(1-benzyl-3-methyl-1,2,3,6-tetrahydropyridin-4-yl)benzoate as a clear oil.

Reference： [1]Patent: US2008/81803,2008,A1 .Location in patent: Page/Page column 45

4
[ 477259-79-3 ]
[ 4334-87-6 ]
[ 699013-97-3 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; at 20 - 80℃; for 4h;	To a solution of (R)-2-chloro-4-[[4-[2-[(trifluoroacetyl)amino]propyl]phenyl]sulfonyl]phenyl trifluoromethanesulfonate (1.0 g) and 3-ethoxycarbonylphenylboronic acid (455 mg) in 1,2-dimethoxyethane (10 ml) were added tetrakis(triphenylphosphine)palladium(0) (104 mg) and 2M sodium carbonate (1.90 ml) at room temperature, and the mixture was stirred at 80 C. for 4 hours. The resulting mixture was poured into water and the aqueous mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel (hexane/ethyl acetate=3:1 to 2:1) to give ethyl(R)-2'-chloro-4'-[[4-[2-[(trifluoroacetyl)amino]propyl]phenyl]sulfonyl]-1,1'-biphenyl-3-carboxylate (783 mg). [0569] NMR (CDCl3, delta): 1.23 (3H, d, J=6.7 Hz), 1.39 (3H, t, J=7.1 Hz), 2.8-3.1 (2H, m), 4.2-4.5 (3H, m), 7.38 (2H, d, J=8.3 Hz), 7.4-7.6 (3H, m), 7.8-8.2 (6H, m) [0570] (+)ESI-MS (m/z): 576 (M+Na)+
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 80℃; for 4h;	To a solution of (R)-2-CHLORO-4- [ [4- [2- [(trifluoroacetyl) amino] propyl] phenyl] sulfonyl] phenyl trifluoromethanesulfonate (1.0 g) and 3- ethoxycarbonylphenylboronic acid (455 mg) in 1,2- dimethoxyethane (10 ml) were added tetrakis (triphenylphosphine) palladium (0) (104 mg) and 2M sodium carbonate (1.90 ml) at room temperature, and the mixture was stirred at 80C for 4 hours. The resulting mixture was poured into water and the aqueous mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel (hexane/ethyl acetate = 3: 1 to 2: 1) to give ethyl (R)-2'-CHLORO-4'- [ [4- [2- [(trifluoroacetyl) amino] propyl] phenyl] sulfonyl]-1, 1'- biphenyl-3-carboxylate (783 mg). NMR (CDC13, 5) : 1.23 (3H, d, J=6.7Hz), 1.39 (3H, t, J=7. 1HZ), 2.8-3. 1 (2H, m), 4.2-4. 5 (3H, m), 7.38 (2H, d, J=8.3Hz), 7.4-7. 6 (3H, m), 7.8-8. 2 (6H, m) (+) ESI-MS (m/z): 576 (M+Na) +

Reference： [1]Patent: US2004/106653,2004,A1 .Location in patent: Page/Page column 21
[2]Patent: WO2004/45610,2004,A1 .Location in patent: Page/Page column 62

5
[ 699013-51-9 ]
[ 4334-87-6 ]
[ 699013-52-0 ]

Yield	Reaction Conditions	Operation in experiment
	With pyridine;copper diacetate; In dichloromethane; at 20℃; for 96h;Molecular sieve;	A mixture of (R)-2,2,2-trifluoro-N-[2-[4-[(4-hydroxyphenyl)thio]phenyl]-1-methylethyl]acetamide (500 mg), 3-ethoxycarbonylphenylboronic acid (546 mg), copper(II) acetate (256 mg), powdered molecular sieves 4 (500 mg) and pyridine (0.569 ml) in dichloromethane (15 ml) was stirred at room temperature for 4 days. After the resulting mixture was filtered with celite, the filtrate was poured into 0.1N hydrochloric acid and the aqueous mixture was extracted with ethyl acetate. The organic layer was washed successively with saturated aqueous sodium bicarbonate and brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel (hexane/ethyl acetate=5:1) to give ethyl(R)-3-[4-[[4-[2-[(trifluoroacetyl)amino]propyl]-phenyl]thio]phenoxy]benzoate (463 mg). [0326] NMR (CDCl3, delta): 1.22 (3H, d, J=6.6 Hz), 1.39 (3H, t, J=6.9 Hz), 2.7-2.95 (2H, m), 4.15-4.45 (3H, m), 6.9-7.85 (12H, m) [0327] (+)ESI-MS (m/z): 526 (M+Na)+
	With pyridine; copper diacetate; In dichloromethane; at 20℃; for 96h;Molecular sieve;	A mixture of (R) -2, 2, 2-TRIFLUORO-N- [2- [4- [ (4- hydroxyphenyl) THIO] PHENYL]-L-METHYLETHYL] ACETAMIDE (500 mg), 3-ethoxycarbonylphenylboronic acid (546 mg), copper (II) 0 acetate (256 mg), powdered molecular sieves 4 A (500 mg) and pyridine (0.569 ml) in dichloromethane (15 ml) was stirred at room temperature for 4 days. After the resulting mixture was filtered with celite, the filtrate was poured into 0. 1N hydrochloric acid and the aqueous mixture was extracted with ethyl acetate. The organic layer was washed successively with saturated aqueous sodium bicarbonate and brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel (hexane/ethyl acetate = 5: 1) to give ethyl (R)-3-[4-[[4-[2-[(trifluoroacetyl)amino]propyl]- phenyl] thio] phenoxy] benzoate (463 mg). NMR (CDC13, 5) : 1.22 (3H, d, J=6.6Hz), 1.39 (3H, t, J=6.9Hz), 2.7-2. 95 (2H, m), 4.15-4. 45 (3H, m), 6.9-7. 85 (12H, m) (+) ESI-MS (m/z): 526 (M+Na) +

Reference： [1]Patent: US2004/106653,2004,A1 .Location in patent: Page/Page column 14
[2]Patent: WO2004/45610,2004,A1 .Location in patent: Page/Page column 39

6
[ 4334-87-6 ]
[ 138647-49-1 ]
[ 782493-24-7 ]

Yield	Reaction Conditions	Operation in experiment
85%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; lithium chloride; In 1,2-dimethoxyethane; for 30h;Reflux; Inert atmosphere;	Example 9A2 ethyl tert-butyl 4-(3-(ethoxycarbonyl)phenyl)-5,6-dihydropyridine- 1 (2H)-carboxylate To a solution of Example 9A1 (2.0g, 6 mmol) and 3- (ethoxycarbonyl)phenylboronic acid (1.6 g, 8.34 mmol), LiCl (1.0 g) and 2M Na2C(¾ solution (1 1 mL) in dimethoxy ethane (100 mL) was added Pd(PPl¾)4 and the resulting mixture was stirred at refluxing temperature for 30 hours under N2. The resulting mixture was cooled to room temperature, stirred overnight, and partially concentrated to remove most of DME. To the remaining aqueous mixture was added dichloromethane, 2M Na2C(¾ solution, and 10 mL NH3.H2O solution. The mixture was extracted with dichloromethane (5 x 300 mL), dried over Na2S04, filtered, and concentrated. The residue was purified by column chromatography on silica gel (petroleum ether: EtOAc =40: 1) to give Example 9A2 in 85% yield as colorless liquid.
	With sodium carbonate; lithium chloride;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; for 3.5h;Heating / reflux;	INTERMEDIATE 32; Step A; To a mixture of tert-butyl 4-[(trifluoromethyl)sulfonyl]oxy}-3,6-dihydropyridine-1(2H)-carboxylate (prepared according to Wustrow, D. J., Wise, L. D., Synthesis, (1991), 993-995.; 10.5 g, 31.6 mmol), 3-(ethoxycarbonyl)phenylboronic acid (8.59 g, 44.3 mmol), lithium chloride (3.98 g, 94.8 mmol), and 2 M Na2CO3 solution (44 mL) in DME (107 mL) was added Pd(PPh3)4 (1.82 g, 1.58 mmol), and the resulting mixture was stirred at reflux under a nitrogen atmosphere for 3.5 h. The reaction mixture was cooled to rt, stirred overnight, then partially concentrated to remove most of the DME. To the remaining aqueous mixture was added DCM, 2M Na2CO3 solution, and 10mL of 28% NH4OH solution. The layers were separated and the organic layer was washed with brine, dried over anhydrous MgSO4, filtered, and concentrated. Purification by flash chromatography (silica, 10% ethyl acetate/hexanes eluent) afforded tert-butyl 4-[3-(ethoxycarbonyl)phenyl]-3,6-dihydropyridine-1(2H)-carboxylate. 1HNMR (CDCl3, 500 MHz): delta 8.07 (s, 1H), 7.95 (d, J=7.5 Hz, 1H), 7.58 (d, J=8.0 Hz, 1H), 7.43 (t, J=8.0 Hz, 1H), 6.13 (br s, 1H), 4.41 (q, J=7.0 Hz, 2H), 4.12 (br s, 2H), 3.68 (t, J=5.5 Hz, 2H), 2.58 (br s, 2H), 1.52 (s, 9H), 1.43 (t, J=7.0 Hz, 3H).
	With sodium carbonate; lithium chloride;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; for 3.5h;Heating / reflux;	INTERMEDIATE 5 Step A : To a mixture of TERT-BUTYL 4- { [ (TRIFLUOROMETHYL) sulfonyl] OXY}-3, 6-DIHYDROPYRIDINE- 1 (2H)-CARBOXYLATE (prepared according to Wustrow, D. J. , Wise, L. D., SYNTLHESIS, (1991), 993-995.; 10.5g, 31. 6MMOL), 3- (ethoxycarbonyl) phenylboronic acid (8.59g, 44. 3MMOL), lithium chloride (3.98g, 94. 8MMOL), and 2 M NA2C03 solution (44ML) in DME (107ML) was added Pd (PPh3) 4 (1.82g, 1. 58mmol), and the resulting mixture was stirred at reflux under a nitrogen atmosphere for 3.5h. The reaction mixture was cooled to rt, stirred overnight, then partially concentrated to remove most of the DME. To the remaining aqueous mixture was added DCM, 2M NA2C03 solution, and-lOmL of 28% NH40H solution. The layers were separated and the organic layer was washed with brine, dried over anhydrous MGS04, filtered, and concentrated. Purification by flash chromatography (silica, 10% ethyl ACETATE/HEXANES ELUENT) AFFORDED TERT-BUTYL4- [3- (ETHOXYCARBONYL) PHENYL] -3, 6-DIHYDROPYRIDINE-1 (2H)- CARBOXYLATE. THNMR (CDC13, 500 MHz): 8 8.07 (s, 1H), 7.95 (d, J = 7. 5 Hz, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.43 (t, J = 8.0 Hz, 1H), 6.13 (br s, 1H), 4.41 (q, J = 7.0 Hz, 2H), 4.12 (br s, 2H), 3.68 (t, J = 5.5 Hz, 2H), 2. 58 (br s, 2H), 1. 52 (s, 9H), 1.43 (t, J = 7.0 Hz, 3H).

		Step A: To a mixture of tert-butyl 4-[(trifluoromethyl)sulfonyl]oxy}-3,6-dihydropyridine-1(2H)-carboxylate (prepared according to Wustrow, D. J., Wise, L. D., Synthesis, (1991), 993-995; 10.5 g, 31.6 mmol), 3-(ethoxycarbonyl)phenylboronic acid (8.59 g, 44.3 mmol), lithium chloride (3.98 g, 94.8 mmol), and 2 M Na2CO3 solution (44 mL) in DME (107 mL) was added Pd(PPh3)4 (1.82 g, 1.58 mmol), and the resulting mixture was stirred at reflux under a nitrogen atmosphere for 3.5 h. The reaction mixture was cooled to rt, stiffed overnight, then partially concentrated to remove most of the DME. To the remaining aqueous mixture was added DCM, 2M Na2CO3 solution, and 10 mL of 28% NH4OH solution. The layers were separated and the organic layer washed with brine, dried over anhydrous MgSO4, filtered, and concentrated. Purification by flash chromatography (silica, 10% ethyl acetate/hexanes eluent) afforded tert-butyl 4-[3-(ethoxycarbonyl)phenyl]-3,6-dihydropyridine-1(2H)-carboxylate. 1HNMR (CDCl3, 500 MHz): delta 8.07 (s, 1H), 7.95 (d, J=7.5 Hz, 1H), 7.58 (d, J=8.0 Hz, 1H), 7.43 (t, J=8.0 Hz, 1H), 6.13 (br s, 1H), 4.41 (q, J=7.0 Hz, 2H), 4.12 (br s, 2H), 3.68 (t, J=5.5 Hz, 2H), 2.58 (br s, 2H), 1.52 (s, 9H), 1.43 (t, J=7.0 Hz, 3H).
2.4 g	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; lithium chloride; In 1,4-dioxane; water; at 100℃; for 3h;Inert atmosphere;	To a mixture of 3-(ethoxycarbonyl)phenylboronic acid (4.0 g, 20.6 mmol), tert-butyl 4-(trifluoromethylsulfonyloxy)-5,6-dihydropyridine-1(2H)-carboxylate (4.0 g, 12 mmol), K2CO3 (4.2 g, 30 mmol), and LiCl (4.3 g, 100 mmol) in p-dioxane (75 mL) and water (15 mL) was added Pd(PPh3)4 (600 mg, 0.5 mmol). The resulting mixture was purged with N2 and then heated to 100 C under N2 for 3 h. After cooling to room temperature, the mixture was diluted with EtOAc and washed with brine. The organic layer was concentrated in vacuo and the residue was purified by flash chromatography (2 to 25% ethyl acetate in hexane as eluent) to give 2.4 g of tert-butyl 4-(3-(ethoxycarbonyl)phenyl)-5,6- dihydropyridine-1(2H)-carboxylate (60% yield) as a light yellow syrup. This was dissolved in EtOH (40 mL), charged with 10% Pd/C (400 mg), and hydrogenated overnight under a H2- balloon at room temperature. The mixture was filtered through celite and the filtrate was concentrated in vacuo to give 2.4 g of tert-butyl 4-(3-(ethoxycarbonyl)phenyl)piperidine-1- carboxylate as a light yellow syrup, which was used directly in the next step. MS: (ES) m/z calculated for C19H28NO4 [M + H]+ 334.2, found 334.2.

Reference： [1]Patent: WO2013/10453,2013,A1 .Location in patent: Page/Page column 101; 102
[2]Patent: US2008/81803,2008,A1 .Location in patent: Page/Page column 46
[3]Bioorganic and Medicinal Chemistry Letters,2008,vol. 18,p. 994 - 998
[4]Patent: WO2004/92124,2004,A2 .Location in patent: Page 58
[5]Patent: US2007/238723,2007,A1 .Location in patent: Page/Page column 29
[6]Patent: WO2016/187393,2016,A1 .Location in patent: Paragraph 0178

7
[ 218610-57-2 ]
[ 4334-87-6 ]
[ 764703-48-2 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 20℃; for 18h;Heating / reflux;	To a solution of 2.5 g (9.8 mmol) of 2-trifluoroethoxyphenyl bromide in 33 MI of toluene at RT was added 0.57 g (0.49 mmol) of tetrakis (triphenyl-phosphine) palladium (0), 0.2 g (10.3 mmol) of 3-ethoxycarbonylphenylboronic acid, 5.9 MI (11.8 mmol) OF 2M aqueous sodium carbonate solution and 17 MI of ethanol. The reaction mixture was heated at reflux for 18 h. The reaction mixture was cooled and diluted with ethyl acetate and water. The organic fraction was separated and washed with saturated NACL solution (brine), dried over MGS04, filtered and the filtrate was concentrated to an oil which was purified by chromatography (silica, 1%, 5%, 30% successively ethyl acetate : hexanes) to give the title compound. Mass Spectrum (ESI) M/E (M+1) : 325.1.

Reference： [1]Patent: WO2004/83189,2004,A1 .Location in patent: Page 37

8
[ 609-73-4 ]
[ 4334-87-6 ]
[ 236102-71-9 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 20 - 80℃; for 18h;	Example 169-1; Ethyl 2'-nitro-3-biphenylylcarboxylate; To a solution of 1-iodo-2-nitrobenzene (2. 0g) and [3- (ethoxycarbonyl) phenyl] boronic acid (2. 0g) in 1,2-dimethoxyethane (20mL), were added tetrakis (triphenyl) palladium (0) (0.93g) and 2M sodium carbonate (8.4mL) at room temperature. The mixture was stirred at 80C for 18 hours. The resulting mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The organic layer was washed successively with saturated aqueous sodium bicarbonate and brine, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel (hexane/ethyl acetate = 10 : 1 to 5 : 1) to give the target'compound (1. 2g). MS ( (+) ESI) m/z : 294 (M+Na) +.

Reference： [1]Patent: WO2005/61475,2005,A2 .Location in patent: Page/Page column 112-113

9
[ 863504-65-8 ]
[ 4334-87-6 ]
[ 863504-70-5 ]

Yield	Reaction Conditions	Operation in experiment
	With copper diacetate; triethylamine; In dichloromethane; at 20℃; under 760.051 Torr; for 48h;Molecular sieve;	Ethyl 3-({3-[(1S)-2-methoxy-(1-methylethyl)oxy}-5-[(1,3-thiazol-2- ylamino) carbonvl] phenyloxy) benzoate; A solution of 3-hydroxy-5-[(1S)-2-methoxy-(1-methylethyl)oxy}-N-1, 3-thiazol-2- ylbenzamide (1.0 g), 3-ethoxycarbonylphenylboronic acid (1.18 g), copper (IT) acetate (1.19 g), triethylamine (2.25 mL) and freshly activated 4A molecular sieves (4g) in DCM (50 mL) was stirred at ambient temperature and under ambient atmosphere for 2 days. The reaction mixture was filtered through diatomaceous earth, washed with DCM (2 x 10 mL), the DCM removed in vacuo, and the residual oil partitioned between ethyl acetate (75 mL) and 1M hydrochloric acid (30 mL). The ethyl acetate layer was separated, washed sequentially with aqueous sodium hydrogen carbonate solution and brine, dried (MgS04), and evaporated to a residue which was chromatographed on silica (eluting with 30% ethyl acetate in isohexane) to give the desired ester (680 mg). 'H NMR 8 (CDC13): 1.3 (d, 3H), 1.4 (t, 3H), 3.4 (s, 3H), 3.5-3. 6 (m, 2H), 4. 35 (q, 2H), 4.5-4. 6 (m, 1H), 6.8 (t, 1H), 6.95 (d, 1H), 7.1 (d, 1H), 7.2 (m, 2H), 7.3 (d, 1H), 7.4 (t, 1H), 7.7 (d, 1H), 7.85 (d, 1H), 11.6 (s, 1H) ; ? 457 (M+H) +

Reference： [1]Patent: WO2005/80359,2005,A1 .Location in patent: Page/Page column 76

10
[ 869500-07-2 ]
[ 4334-87-6 ]
[ 869500-08-3 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; toluene; for 3h;Heating / reflux;	A mixture of <strong>[869500-07-2]1-bromo-2-iodo-3-methylbenzene</strong> (0.46g), {3-[(ethyloxy)- carbonyl] phenyl}boronic acid (0.20g), tetrakis(triphenylphosphine)palladium(0) (60mg), potassium carbonate (0.71g), toluene (6ml) and ethanol (6ml) was stirred under reflux under nitrogen for 3h. The mixture was partitioned between water (40ml) and ether (40ml) and the aqueous layer extracted with ether (15ml). The combined ether extracts were dried (MgS04), evaporated and the residue purified by flash chromatography eluting with 2% ethyl acetate in isohexane to afford the title compound (0.22g). LC/MS Rt = 4.1 min, [MH+] 319/321.

Reference： [1]Patent: WO2005/108369,2005,A1 .Location in patent: Page/Page column 49

11
[ 872989-55-4 ]
[ 201230-82-2 ]
[ 4334-87-6 ]
[ 872991-27-0 ]

Yield	Reaction Conditions	Operation in experiment
30%	With potassium carbonate;bis-triphenylphosphine-palladium(II) chloride; In methoxybenzene; at 80℃; for 5h;	Example 56: 3-[2-(2-Methoxy-5-thien-2-yl-phenyl)-acryloyl]-benzoic acid[0460] Ex-56A: In a 25 mL 2-neck round-bottom flask, 2-(3-bromomethyl-4-methoxy- phenyl)-thiophene obtained from Ex-7D (250 mg, 0.88 mmol), K2CO3 (370 mg, 2.68 mmol), 3-ethoxycarbonylphenylboronic acid (190 mg, 0.98 mmol) and bis(triphenylphospine) palladium (II) chloride (19 mg, 0.027 mmol) were combined and the round bottom was flushed with carbon monoxide for 5 min. Anisole (5 mL) was added and the resulting solution was heated to 80 0C under carbon monoxide. After 5 h the reaction was cooled to room temperature, diluted with MTBE and H2O and the layers were cut. The organic layer was concentrated to dryness and the crude was purified by silica gel chromatography (15% EtOAc in hexanes) to afford 100 mg (30% yield) of desired 3-[2-(2-methoxy-5-thien-2-yl-phenyl)-acetyl]-benzoic acid ethyl ester. 1H-NMR (300 MHz, CDCl3): delta 8.72-8.74 (m, IH), 8.21-8.25 (m, 2H), 7.56 (d, J = 8.3 Hz, IH), 7.44-7.52 (m, 2H), 7.17-7.21 (m, 2H), 7.01-7.04 (m, IH), 6.90 (d, J = 7.9 Hz, IH), 4.42 (q, J= 7.1 Hz, 2H), 4.34 (s, 2H), 3.82 (s, 3H). 1.41 (t, J= 7.1 Hz, 3H).

Reference： [1]Patent: WO2006/4903,2006,A2 .Location in patent: Page/Page column 180-181

12
[ 75415-78-0 ]
[ 4334-87-6 ]
[ 612832-85-6 ]

Yield	Reaction Conditions	Operation in experiment
30%	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; at 80℃; for 18h;	ExamPle 1 : {2- [5-chloro-2- (benzvloxy)-phenvll-cyclopent-1-envl}-benzoic acid a) 3-(2-Bromocyclopent-1-envl)-benzoic acid ethyl ester 1, 2-Dibromocyclopentene (Ex Aldrich, 27,732-0) (5g, 0.0221 mol), (3- ethoxycarbonylphenyl) boronic acid (Ex Combiblocks inc. BB-2117-005) (4. 26g, 0.0221 mol), Pd (O) [PPh3] 4 (0. 5g) and potassium carbonate (5g) were stirred at 80C under nitrogen for 18h in dimethoxyethane (30mL). The reaction mixture was then filtered through Kieselguhr and evaporated down to an oil. Purification was carried out on a Biotage (90g column) using iso-hexane containing a gradient of dichloromethane (0-30%) to give the required product (wt: 1. 15g i. e. 30% yield) 'H NMR (400MHz, CDCI3) 1.40 (3H, t, J=7Hz), 2.00-2. 12 (2H, m), 2.75-2. 94 (4H, m's), 4.39 (2H, q, J=7Hz), 7.43 (1 H, t, J=8Hz), 7.85 (1 H, d, J=8Hz), 7.96 (1 H, d, J=8Hz), 8.22 (1 H, s). LC/MS rt 3. 82, [MH+] 295,297.

Reference： [1]Patent: WO2003/84917,2003,A1 .Location in patent: Page/Page column 26; 28; 61-62

13
N-[(1,2)-cis-4-bromo-2-methoxycyclohex-3-en-1-yl]-3,4-dichloro-5-methyl-1H-pyrrole-2-carboxamide [ No CAS ]
[ 4334-87-6 ]
3-((3,4-cis)-4-[(3,4-dichloro-5-methyl-1H-pyrrol-2-yl)carbonyl]amino}-3-methoxycyclohex-1-en-1-yl)benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate;PS-PPh3-Pd resin; In 1,2-dimethoxyethane; ethanol; water; at 150℃;Microwave irradiation;	Example 11; 3 -((3 A-Cis)-4- i IY3 ^-Dichloro-S-methyl- 1 H-pyrrol-2-yl)carbonyll amino -3 - methoxycyclohex- 1 -en- 1 -vDbenzoic acid; N- [( 1 ,2)-cis-4-Bromo-2-methoxy cyclohex-3 -en- 1 -y 1] -3 ,4-dichloro-5 -methyl- 1 H- pyrrole-2-carboxamide (Intermediate 26; 100 mg, 0.262 mmol), (3- ethoxycarbonylphenyl)boronic acid (61 mg, 0.31 mmol), PS-PPh3-Pd (resin, 0.11 mmol/g, 240 mg, 0.026 mmol) and potassium carbonate (127 mg, 0.92 mmol) were suspended in a mixture of DME/EtOH/H2theta (2:2:1, 4 ml) in a sealed tube. The reaction mixture was heated to 150 C under microwave conditions, cooled down to room temperature and filtered. The filter cake was washed with ethyl acetate (10 ml) and water (5 ml), the combined aqueous layer was acidified to pH 2 with 2M HCl, and extracted with ethyl acetate (2x10 ml), the combined organic layer was dried, concentrated under vacuum and purified by column chromatography (5% tol5% gradient MeOH in ethyl acetate) giving the title compound as an off white solid (6 mg). M.p.255 0C. NuMR: 1.87 (m, 2H), 2.19 (s, 3H), 2.51 (m, 2H), 3.42 (s, 3H), 4.05 (m, IH), 4.27 (m, IH), 6.31 (m, IH), 7.12 (d, IH), 7.50 (t, IH), 7.78 (d, IH), 7.85 (d, IH), 7.98 (s, IH), 12.17 (br s, IH), 13.05 (br s, IH). MS (ESNu): 423.24 (M-) for C20H20Cl2N2O4.

Reference： [1]Patent: WO2006/87548,2006,A2 .Location in patent: Page/Page column 49

14
[ 626-05-1 ]
[ 4334-87-6 ]
[ 884656-92-2 ]

Yield	Reaction Conditions	Operation in experiment
20%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; acetonitrile; at 80℃; for 12h;	A solution of 2,6-dibromopyridine (6.16 g, 26 mmol) and 3- carboethoxybenzeneboronic acid (0.5 g, 2.6 mmol) in acetonitrile (20 niL) is treated with a solution of sodium carbonate (0.88 g) in water (5 mL). The mixture is degassed twice, and a catalytic amount of tetrakis(triphenylphosphine)palladiurn is added. The reaction mixture is heated to 80 C and stirred for 12 h., then cooled, filtered and evaporated. The residue is partitioned between water and ethyl acetate, and the organic phase is washed with satd. aq. brine, dried over sodium sulfate, filtered and evaporated. The residual material is separated by column chromatography to give ethyl 3-(6-bromo-pyridin-2-yl)- benzoate (154 nig, 20%).

Reference： [1]Patent: WO2006/44505,2006,A2 .Location in patent: Page/Page column 104

15
[ 1120-87-2 ]
[ 4334-87-6 ]
[ 4385-74-4 ]

Yield	Reaction Conditions	Operation in experiment
86%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; acetonitrile; for 12h;Heating / reflux;	A solution of 4-bromopyridine (1.0 g, 5.2 mmol) in acetonitrile-water (10 m.L/5 mL) is treated with 3-carboethoxybenzeneboronic acid (0.93 g, 5.2 mmol), sodium carbonate (2.2 g, 21 mmol) and catalytic tetrakis(triphenylphosphine)palladium. The solution is heated to reflux for 12 h., then cooled and extracted with ethyl acetate. The extract is washed with brine, dried over sodium sulfate, filtered and evaporated. The residual material is separated by flash chromatography to afford ethyl 3-pyridin-4-yl- benzoate (1.0 g, 86%).

Reference： [1]Patent: WO2006/44505,2006,A2 .Location in patent: Page/Page column 102

16
[ 884656-85-3 ]
[ 4334-87-6 ]
ethyl 3-[4-(4-isopropyl-phenyl)-pyridin-2-yl]-benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; acetonitrile; for 12h;Heating / reflux;	A solution of 2-chloro-4-(4-isopropyl-phenyl)-pyridine (110 mg, 0.48 mmol) in acetonitrile-water (1 mL/0.5 mL) is treated with 3-carboethoxybenzeneboronic acid (186 mg, 0.96 mmol), sodium carbonate (153 mg, 1.44 mmol) and tetrakis(triphenylphosphine)palladium (cat. amount). The mixture is heated to reflux for 12 h., then cooled and partitioned between water and ethyl acetate. The organic phase is washed with brine, dried over magnesium sulfate, filtered and evaporated. The residue is separated by column chromatography to afford ethyl 3-[4-(4-isopropyl-phenyl)-pyridin- 2-yl] -benzoate ( 116 mg, 70%) .

Reference： [1]Patent: WO2006/44505,2006,A2 .Location in patent: Page/Page column 100

17
[ 884656-88-6 ]
[ 4334-87-6 ]
ethyl 3-[5-(4-isopropyl-phenyl)-pyridin-3-yl]-benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 80℃;	A solution of 3-bromo-5-(4-isopropyl-phenyl)-pyridine (300 mg, 1.1 mmol) and 3-carboethoxybenzeneboronic acid (180 mg, 1.1 mmol) in ethanol-toluene- water (10 mL/5 mL/3 mL) is treated with sodium carbonate (345 mg), degassed twice and treated with a catalytic quantity of tetrakis(triphenylphosphine)palladium. The mixture is heated to 80 C with stirring until the starting material is consumed as determined by TLC. Then, the mixture is cooled, filtered and evaporated, and the residual material is partitioned between water and ethyl acetate. The organic phase is washed with brine, dried over sodium sulfate, filtered and evaporated, and the residue is EPO <DP n="103"/>separated by column chromatography to afford ethyl 3-[5-(4-isopropyl-phenyl)-pyridin- 3-yl]-benzoate (252 mg, 79%).

Reference： [1]Patent: WO2006/44505,2006,A2 .Location in patent: Page/Page column 101-102

18
[ 942600-09-1 ]
[ 4334-87-6 ]
4'-(7-cyano-6-methyl-2,4-dioxo-1,2,4,5-tetrahydro-3H-pyrrolo[3,2-d]pyrimidin-3-yl)biphenyl-3-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		3-(4-Bromophenyl)-6-methyl-254-dioxo-2,3,4,5-tetrahydro-li/-pyrrolo[352- fiOpyrimidine-7-carbonitrile (Intermediate 4) (50 mg, 0.15 mmol), (3- ethoxycarbonylphenyl)boronic acid (30 mg, 0.15 mmol), PS-PPh3-Pd (resin, 136 mg, 0.11 mmol/g, 0.015 mmol) and potassium carbonate (69 mg, 0.5 mmol) were suspended in DME/EtOH/H2O(2:2:l, 4 ml) in a micro-reaction tube. The mixture was heated to 12O0C in a microwave for 30 minutes and then cooled to room temperature. The reaction mixture was filtered and the filter cake was washed with water (5 ml). The combined aqueous filtrates were washed with diethyl ether. The aqueous layer was acidified (2M HCl) to pH = 2 and extracted with ethyl acetate (2 x 10 ml). The combined organic layers were concentrated and purified by flash column chromatography eluted with 15% methanol in dichloromethane to give the desired product as an off-white solid (32 mg). MS (ES): 387 (MH+) for C2JH14N4O41H-NMR delta: 2.40 (s5 3H); 7.38 (d, 2H); 7.67 (t, IH); 7.80 (d, 2H); 7.96 (d, 2H); 8.24 (s, IH); 12.05 (s, IH); 12.96 (s, IH); 13.12 (br, IH).

Reference： [1]Patent: WO2007/71965,2007,A2 .Location in patent: Page/Page column 29

19
[ 1016644-41-9 ]
[ 4334-87-6 ]
[ 885068-65-5 ]

Yield	Reaction Conditions	Operation in experiment
	With caesium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; at 90℃; for 6.16667h;	CS2CO3 solution (407 mg, 1.25 mmol in 2 mL water) is added to a stirred solution of (6-chloro-2- methoxy-pyrimidin-4-yl)-[2-(2,4-dichloro-phenyl)-ethyl]-amine (166 mg, 0.5 mmol) and ethylcarbonylphenyl boronic acid (135.8 mg, 0.7 mmol) in 1 ,2-dimethoxyethane (5 mL). The mixture is degassed over nitrogen for 10 minutes, tetrakis(triphenylphosphine)palladium (0) (23 mg, 0.02 mmol) is added and the reaction mixture is refluxed at 9O0C for 6 hours. The reaction is cooled to room temperature, diluted with water (10 mL), filtered over a pad of Celite and the volatiles are removed under reduced pressure. The aqueous pH is adjusted to neutral (0.1 N HCl) and extracted twice with ethyl acetate. The combined extracts are washed with brine and water, dried over magnesium sulfate, filtered and concentrated in reduced pressure. The crude residue is purified by chromatography (SiO2 packed column), eluting with 5-15% Ethyl acetate/DCM to afford 3-\|6-['2-(2,4- dichloro-phenyl)-ethylamino]-2-methoxy-pyrimidin-4-yl) -benzoic acid ethyl ester (48 mg, Example 77). LCMS: Rtau = 2.95 minutes, MS: 447 (M+H); 1H NMR, (300 MHz, CDCl3): delta 8.65 (IH, s), 8.3 (IH, d, J=3.5Hz), 8.15 (IH, d, J=3.5Hz), 7.55 (IH, t, J=3.5Hz), 7.45 (IH, s), 7.25 (2H, s), 6.5 (IH, s), 4.95 (IH, b), 4.45 (2H, q, J=3.5Hz), 4.05 (3H, s), 3.75 (2H, b), 3.1 (2H, t, J=3.5Hz), 1.45 (3H, t, 3.5Hz). IC50 = 149 nM

Reference： [1]Patent: WO2008/39882,2008,A1 .Location in patent: Page/Page column 199

20
[ 1207968-95-3 ]
[ 4334-87-6 ]
[ 1207968-96-4 ]

Yield	Reaction Conditions	Operation in experiment
55%	With potassium tert-butylate;Neolyst CX-32; In 1,2-dimethoxyethane; at 90℃; for 13h;	A mixture of 8-chloro-2-[3-(trifluoromethyl)benzyl]-1,2,3,4-tetrahydroisoquinoline (0.36 g, 1.0 mmol) obtained in Reference Example 1, <strong>[4334-87-6][3-(ethoxycarbonyl)phenyl]boronic acid</strong> (0.23 g, 1.2 mmol), Neolyst CX-32 (cinnamylchloro[1,3-bis-(diisopropylphenyl)-2-imidazolidinylidene]palladium (II)) (19.5 mg, 0.03 mmol), and potassium tert-butoxide (0.26 g, 2.3 mmol) in dimethoxyethane (5 mL) was stirred for 13 hours at 90 C. The reaction solution was diluted with saturated aqueous sodium bicarbonate and extracted with ethyl acetate. The extract was washed with water and dried over anhydrous magnesium sulfate, and the solvent was then distilled off at reduced pressure. The residue was purified by silica gel column chromatography (hexane-ethyl acetate=10:1) to give 0.24 g of the titled compound (yield 55%) in the form of an oily substance.1H-NMR (CDCl3) delta: 1.39 (3H, t, J=7.2 Hz), 2.68 (2H, t, J=6.0 Hz), 2.96 (2H, t, J=6.0 Hz), 3.51 (1H, s), 3.61 (3H, s), 4.38 (2H, q, J=7.2 Hz), 7.03 (1H, d, J=7.2 Hz), 7.14 (1H, d, J=7.8 Hz), 7.20 (1H, d, J=7.5 Hz), 7.30-7.50 (5H, m), 7.54 (1H, s), 7.95 (1H, s), 7.97-8.05 (1H, m).

Reference： [1]Patent: US2010/41891,2010,A1 .Location in patent: Page/Page column 42; 43

21
[ 1171926-64-9 ]
[ 4334-87-6 ]
[ 1207970-52-2 ]

Yield	Reaction Conditions	Operation in experiment
95%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 80℃; for 15h;	A mixture of (7-bromo-1-benzothiophen-2-yl)methanol (1.8 g, 7.40 mmol) obtained in Reference Example 162, <strong>[4334-87-6][3-(ethoxycarbonyl)phenyl]boronic acid</strong> (1.72 g, 8.88 mmol), tetrakis(triphenylphosphine)palladium (0) (0.26 g, 0.22 mmol), sodium carbonate (1.57 g, 14.8 mmol), water (10 mL), and dimethoxyethane (30 mL) was stirred for 15 hours at 80 C. The reaction solution was diluted with water and extracted with ethyl acetate. The extract was washed with water and dried over anhydrous magnesium sulfate, and the solvent was then distilled off at reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=3:1) to give 2.20 g of the titled compound (yield 95%) in the form of an oily substance.1H NMR (CDCl3) delta: 1.41 (3H, t, J=7.2 Hz), 1.93 (1H, t, J=6.0 Hz), 4.41 (2H, q, J=7.2 Hz), 4.93 (2H, d, J=6.0 Hz), 7.30 (1H, s), 7.36 (1H, d, J=6.9 Hz), 7.45 (1H, t, J=7.5 Hz), 7.56 (1H, t, J=7.8 Hz), 7.74 (1H, d, J=7.8 Hz), 7.91 (1H, d, J=7.8 Hz), 8.08 (1H, d, J=7.8 Hz), 8.36 (1H, s).

Reference： [1]Patent: US2010/41891,2010,A1 .Location in patent: Page/Page column 64
[2]Journal of Medicinal Chemistry,2014,vol. 57,p. 5226 - 5237

22
[ 1207968-97-5 ]
[ 4334-87-6 ]
[ 1207968-98-6 ]

Yield	Reaction Conditions	Operation in experiment
92%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 90℃; for 20h;Inert atmosphere;	A mixture of the 5-bromo-2-[3-(trifluoromethyl)benzyl]-1,2,3,4-tetrahydroisoquinoline (4.76 g, 12.9 mmol) obtained in Reference Example 3, <strong>[4334-87-6][3-(ethoxycarbonyl)phenyl]boronic acid</strong> (3.01 g, 15.5 mmol), and tetrakis(triphenylphosphine)palladium (0) (601 mg, 0.52 mmol) in 2 N sodium carbonate aqueous solution (25.8 mL)-1,2-dimethoxyethane (50 mL) was reacted for 20 hours at 90 C. in a nitrogen atmosphere. The addition of saturated saline to the reaction solution was followed by extraction with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate, and then concentrated at reduced pressure. The residue was purified by silica gel column chromatography to give 5.20 g of the titled compound (yield 92%) in the form of an oily substance.1H-NMR (CDCl3) delta: 1.39 (3H, t, J=7.2 Hz), 2.62-2.77 (4H, m), 3.72 (4H, s), 4.38 (2H, q, J=7.0 Hz), 7.04 (1H, d, J=7.5 Hz), 7.06-7.12 (1H, m), 7.16-7.24 (1H, m), 7.41-7.56 (4H, m), 7.60 (1H, d, J=7.5 Hz), 7.67 (1H, s), 7.98-8.05 (2H, m).

Reference： [1]Patent: US2010/41891,2010,A1 .Location in patent: Page/Page column 43

23
[ 1207969-03-6 ]
[ 4334-87-6 ]
[ 1207969-05-8 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 90℃; for 16h;Inert atmosphere;	A mixture of 4-bromo-2-[3-(trifluoromethyl)benzyl]-1-benzofuran (3.40 g, 9.58 mmol) obtained in Reference Example 4, <strong>[4334-87-6][3-(ethoxycarbonyl)phenyl]boronic acid</strong> (2.23 g, 11.5 mmol), and tetrakis(triphenylphosphine)palladium (0) (553 mg, 0.48 mmol) in 2 N sodium carbonate aqueous solution (30 mL)-1,2-dimethoxyethane (30 mL) was reacted for 16 hours at 90 C. in a nitrogen atmosphere. The addition of water to the reaction solution was followed by extraction with ethyl acetate. The organic layer was washed with saturated saline, then dried over anhydrous sodium sulfate, and then concentrated at reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate-hexane 2:3) to give 3.30 g of 3-[2-[3-(trifluoromethyl)benzyl]-1-benzofuran-4-yl]benzoic acid. 2 N sodium hydroxide aqueous solution (8 mL, 16 mmol) was added at room temperature to an ethanol (50 mL) solution of this compound, the mixture was stirred for 2 hours at 60 C., and the product was concentrated at reduced pressure. The reaction solution was made acidic with the addition of water and hydrochloric acid, and was extracted with ethyl acetate. The organic layer was washed with water and saturated saline, and then dried over anhydrous sodium sulfate. The solvent was distilled off at reduced pressure, and the resulting residue was crystallized from ethyl acetate-hexane to give 2.3 g of the titled compound (yield 61%). Melting point: 138-139 C. (ethyl acetate-hexane).1H-NMR (CDCl3) delta: 4.19 (2H, s), 6.63 (1H, s), 7.20-7.78 (8H, m), 7.85 (1H, dd, J=7.8, 1.2 Hz), 8.13 (1H, dd, J=7.8, 1.2 Hz), 8.37 (1H, s), 1H unconfirmed.
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 90℃; for 16h;Inert atmosphere;	A mixture of 4-bromo-2-[3-(trifluoromethyl)benzyl]-1-benzofuran obtained in Reference Example 77 (3.40 g, 9.58 mmol), <strong>[4334-87-6](3-(ethoxycarbonyl)phenyl)boronic acid</strong> (2.23 g, 11.5 mmol), tetrakis(triphenylphosphine)palladium(0) (553 mg, 0.48 mmol) in 2N aqueous sodium carbonate solution (30 mL)-1,2-dimethoxyethane (30 mL) was reacted for 16 hr at 90C under a nitrogen atmosphere. To the reaction mixture was added water, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate-hexane 2:3) to give ethyl 3-[2-[3-(trifluoromethyl)benzyl]-1-benzofuran-4-yl]benzoate (3.30 g). To a solution of the compound in ethanol (50 mL) was added 2N aqueous sodium hydroxide solution (8 mL, 16 mmol) at room temperature, and the mixture was stirred for 2 hr at 60C, and concentrated under reduced pressure. To the reaction mixture were added water and hydrochloric acid to acidify the aqueous layer, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and evaporated under reduced pressure. The obtained residue was crystallized from ethyl acetate-hexane to give the title compound (2.3 g, yield 61%). melting point 138 - 139C (ethyl acetate-hexane). 1H-NMR (CDCl3) delta: 4.19 (2 H, s), 6.63 (1 H, s), 7.20 - 7.78 (8 H, m), 7.85 (1 H, dd, J = 7.8, 1.2 Hz), 8.13 (1 H, dd, J = 7.8, 1.2 Hz), 8.37 (1 H, s), 1 H unconfirmed.

Reference： [1]Patent: US2010/41891,2010,A1 .Location in patent: Page/Page column 44
[2]Patent: EP2518054,2012,A1 .Location in patent: Page/Page column 63
[3]Journal of Medicinal Chemistry,2014,vol. 57,p. 5226 - 5237

24
[ 1207970-19-1 ]
[ 4334-87-6 ]
[ 1207970-21-5 ]

Yield	Reaction Conditions	Operation in experiment
49%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 95℃; for 4h;Inert atmosphere;	2-[[3-(Trifluoromethyl)phenyl]amino][1,2,4]triazolo[1,5-a]pyridin-8-yl trifluoromethanesulfonate (590 mg, 1.38 mmol) obtained in Reference Example 120, <strong>[4334-87-6][3-(ethoxycarbonyl)phenyl]boronic acid</strong> (295 mg, 1.52 mmol), and tetrakis(triphenylphosphine)palladium (0) (192 mg, 0.166 mmol) in 2 N sodium carbonate aqueous solution (2.1 mL)-1,2-dimethoxyethane (12 mL) mixture were stirred for 4 hours at 95 C. in a nitrogen atmosphere. Water was poured into the reaction solution, and the mixture was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous magnesium sulfate, and the solvent was distilled off at reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane=3:7) to give 291 mg of the titled compound (yield 49%) in solid form.1H-NMR (CDCl3) delta: 1.41 (3H, t, J=7.2 Hz), 4.42 (2H, q, J=7.2 Hz), 7.00-7.07 (1H, m), 7.19-7.33 (2H, m), 7.42 (1H, t, J=7.9 Hz), 7.59 (1H, t, J=7.9 Hz), 7.63-7.72 (2H, m), 7.98-8.02 (1H, m), 8.06-8.11 (1H, m), 8.27-8.33 (1H, m), 8.49 (1H, dd, J=6.8, 1.1 Hz), 8.61 (1H, t, J=1.1 Hz).

Reference： [1]Patent: US2010/41891,2010,A1 .Location in patent: Page/Page column 57

25
[ 4334-87-6 ]
[ 93103-83-4 ]
[ 1207970-51-1 ]

Yield	Reaction Conditions	Operation in experiment
91%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; for 3h;Reflux; Inert atmosphere;	A 2 M sodium carbonate aqueous solution (2.8 mL)-1,2-dimethoxyethane (15 mL) mixed solution of (4-bromo-1-benzothiophen-2-yl)methanol (341 mg, 1.40 mmol) obtained in Reference Example 161, <strong>[4334-87-6][3-(ethoxycarbonyl)phenyl]boronic acid</strong> (327 mg, 1.68 mmol), and tetrakis(triphenylphosphine)palladium (0) (65 mg, 0.056 mmol) was heated to reflux for 3 hours in a nitrogen atmosphere. The reaction solution was diluted with saturated brine and ethyl acetate, and was filtered using celite. The resulting filtrate was extracted with ethyl acetate. The combined organic layers were dried over anhydrous sodium sulfate, and then concentrated at reduced pressure, and the residue was purified by silica gel column chromatography (hexane-ethyl acetate 85:15?67:33) to give 399 mg of the titled compound (yield 91%).1H-NMR (CDCl3) delta: 1.39 (3H, t, J=7.1 Hz), 2.13 (1H, br s), 4.39 (2H, q, J=7.1 Hz), 4.89 (2H, br s), 7.25 (1H, d, J=3.3 Hz), 7.30-7.43 (2H, m), 7.53 (1H, t, J=7.7 Hz), 7.68-7.75 (1H, m), 7.82 (1H, d, J=7.7 Hz), 8.04-8.09 (1H, m), 8.21 (1H, t, J=1.6 Hz).

Reference： [1]Patent: US2010/41891,2010,A1 .Location in patent: Page/Page column 64
[2]Journal of Medicinal Chemistry,2014,vol. 57,p. 5226 - 5237

26
[ 1207970-48-6 ]
[ 4334-87-6 ]
[ 1207970-54-4 ]

Yield	Reaction Conditions	Operation in experiment
80%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; for 9h;Reflux;	A mixture of (7-bromo-4-fluoro-1-benzothiophen-2-yl)methanol (800 mg, 30.6 mmol) synthesized in Reference Example 164, <strong>[4334-87-6][3-(ethoxycarbonyl)phenyl]boronic acid</strong> (713 mg, 36.8 mmol), and tetrakis(triphenylphosphine)palladium (0) (177 mg, 0.153 mmol) in 2 N sodium carbonate aqueous solution (30 mL)-1,2-dimethoxyethane (30 mL) was heated to reflux for 9 hours. The reaction solution was diluted with saturated brine and ethyl acetate, and was filtered using celite. The resulting filtrate was extracted with ethyl acetate. The combined organic layers were dried over anhydrous sodium sulfate and then concentrated at reduced pressure, and the residue was purified by silica gel column chromatography (hexane-ethyl acetate 100:0?40:60) to give 810 mg of the titled compound (yield 80%). Melting point: 89-90 C.1H-NMR (CDCl3) delta: 1.41 (3H, t, J=7.1 Hz), 1.95 (1H, t, J=6.0 Hz), 4.41 (2H, q, J=7.1 Hz), 4.94 (2H, dd, J=6.2, 1.0 Hz), 7.12 (1H, dd, J=9.6, 8.2 Hz), 7.31 (1H, dd, J=8.1, 4.8 Hz), 7.40-7.42 (1H, m), 7.56 (1H, t, J=7.7 Hz), 7.86 (1H, dq, J=7.7, 1.0 Hz), 8.09 (1H, dt, J=7.9, 1.4 Hz), 8.31 (1H, t, J=1.8 Hz).

Reference： [1]Patent: US2010/41891,2010,A1 .Location in patent: Page/Page column 64
[2]Journal of Medicinal Chemistry,2014,vol. 57,p. 5226 - 5237

27
[ 1207970-77-1 ]
[ 4334-87-6 ]
[ 1207970-87-3 ]

Yield	Reaction Conditions	Operation in experiment
72%	With potassium phosphate;palladium diacetate; XPhos; In tetrahydrofuran; at 75℃; for 28h;	A mixture of the 7-chloro-4-fluoro-2-[3-(methylsulfonyl)benzyl]-1-benzothiophene (0.67 g, 1.89 mmol) obtained in Reference Example 194, <strong>[4334-87-6][3-(ethoxycarbonyl)phenyl]boronic acid</strong> (0.44 g, 2.27 mmol), palladium acetate (12.7 mg, 0.057 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropyl biphenyl (X-Phos) (53.9 mg, 0.11 mmol), and potassium phosphate (0.80 g, 3.78 mmol) in THF (15 mL) was stirred for 28 hours at 75 C. The reaction solution was diluted with water and extracted with ethyl acetate. The extract was washed with water and dried over anhydrous magnesium sulfate, and the solvent was then distilled off at reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=3:1-3:2) to give 0.78 g of the titled compound (yield 88%) in the form of an oily substance.1H NMR (CDCl3) delta: 1.40 (3H, t, J=7.2 Hz), 3.04 (3H, s), 4.31 (2H, s), 4.40 (2H, q, J=7.2 Hz), 7.11 (1H, t, J=9.0 Hz), 7.20-7.35 (2H, m), 7.45-7.60 (3H, m), 7.75-7.90 (3H, m), 8.06 (1H, d, J=7.5 Hz), 8.28 (1H, s).

Reference： [1]Patent: US2010/41891,2010,A1 .Location in patent: Page/Page column 69

28
[ 1207970-79-3 ]
[ 4334-87-6 ]
ethyl 3-[2-[3-fluoro-5-(methylsulfonyl)benzyl]-1-benzothiophen-7-yl]benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With potassium phosphate;palladium diacetate; XPhos; In tetrahydrofuran; for 24h;Reflux;	A mixture of 7-chloro-2-[3-fluoro-5-(methylsulfonyl)benzyl]-1-benzothiophene (0.7 g, 1.97 mmol) obtained in Reference Example 196, <strong>[4334-87-6][3-(ethoxycarbonyl)phenyl]boronic acid</strong> (0.46 g, 2.37 mmol), palladium acetate (13.3 mg, 0.059 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropyl biphenyl (56.4 mg, 0.12 mmol), potassium phosphate (0.84 g, 3.95 mmol), and THF (15 mL) was heated to reflux for 24 hours. The reaction solution was diluted with water and extracted with ethyl acetate. The extract was washed with water and dried over anhydrous magnesium sulfate, and the solvent was then distilled off at reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=3:2) to give 0.70 g of the titled compound (yield 76%) in the form of an oily substance.1H NMR (CDCl3) delta: 1.39 (3H, t, J=7.2 Hz), 3.05 (3H, s), 4.30 (2H, s), 4.40 (2H, q, J=7.2 Hz), 7.17 (1H, s), 7.20-7.35 (1H, m), 7.35 (1H, d, J=7.2 Hz), 7.45 (1H, t, J=7.8 Hz), 7.56 (1H, d, J=7.8 Hz), 7.50-7.60 (1H, m), 7.66 (1H, s), 7.71 (1H, d, J=7.8 Hz), 7.86 (1H, d, J=7.5 Hz), 8.07 (1H, d, J=8.1 Hz), 8.33 (1H, s).

Reference： [1]Patent: US2010/41891,2010,A1 .Location in patent: Page/Page column 76

29
[ 4334-87-6 ]
[ 30289-28-2 ]
[ 1207738-73-5 ]

Reference： [1]Journal of Organic Chemistry,2010,vol. 75,p. 1251 - 1258

30
[ 109-04-6 ]
[ 4334-87-6 ]
[ 4550-32-7 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; toluene; at 20 - 100℃;Sealed; Microwave irradiation;	Preparation of i-2bStep A; Preparation of ethyl 3-pyridin-2-ylbenzoate (i-2a) Tetrakis(triphenylphosphine)pailadium(0) (208 mg, 0.180 mmol) was added to a solution of 3-ethoxycarbonylphenyl boronic acid (350 nig, 1.80 mmol), 2-bromorhoyridine (189 muL, 1.99 mmol) and potassium carbonate (499 mg, 3.61 mmol) in EtOH:toluene (4,00 niL of an 80:20 mixture, respectively) at rt. The resulting solution was heated to 100 C in a sealed microwave vial for a total of 15 min. After cooling to rt, the reaction mixture was filtered through a short column of Celite, eluting with EtOAc. The filtrate was washed with water and brine, dried (sodium sulfate) and concentrated in vacuo. The crude residue was purified by flash chromatography on silica gel (isocratic elution; 10% EtOAc/hexanes as eluent) to afford the title compound Wa. m/z (ES) 228 (MH)+.

Reference： [1]Patent: WO2010/77624,2010,A1 .Location in patent: Page/Page column 34-35
[2]Organic Letters,2015,vol. 17,p. 1513 - 1516

31
[ 3017-70-7 ]
[ 4334-87-6 ]
ethyl 3-(3-methylbut-2-en-2-yl)benzoate [ No CAS ]

Reference： [1]Advanced Synthesis and Catalysis,2010,vol. 352,p. 2081 - 2084

32
[ 950738-61-1 ]
[ 4334-87-6 ]
[ 1213233-21-6 ]

Yield	Reaction Conditions	Operation in experiment
		Step 1: To N-[3-(3-bromo-pyrazolo[1,5-a]pyrimidin-7-yl)-phenyl]-3-trifluoromethyl-benzamide (500 mg, 1.08 mmol), Pd(PPh3)4 (63 mg, 0.054 mmol), K2CO3 (2M solution, 1.6 ml, 3.2 mmol) and DME (5 ml) are added. The mixture is stirred at room temperature for 30 minutes, and then 3-ethoxycarbonylphenylboronic acid (316 mg, 1.63 mmol) is added. The reaction is heated at 85 C. overnight, then DME is evaporated. The residue is diluted with water and extracted with CH2Cl2+5% MeOH. The obtained crude is purified by a silica gel column chromatography (eluent: gradient from CH2Cl2 to CH2Cl2-MeOH 96:4). 3-{7-[3-(3-Trifluoromethyl-benzoylamino)-phenyl]-pyrazolo[1,5-a]pyrimidin-3-yl}-benzoic acid ethyl ester is used in next step without further purification.

Reference： [1]Patent: US2007/219186,2007,A1 .Location in patent: Page/Page column 40

33
[ 3934-20-1 ]
[ 4334-87-6 ]
[ 7417-21-2 ]
[ 1185999-57-8 ]
[ 1185999-59-0 ]

Yield	Reaction Conditions	Operation in experiment
9%; 31%		Reference Example 20; Ethyl 3-(2-(2-(3,4-dimethoxyphenyl)ethoxy)pyrimidin-4-yl)benzoate and ethyl 3-(4-(2-(3,4-dimethoxyphenyl)ethoxy)pyrimidin-2-yl)benzoate; Sodium hydride (60% liquid paraffin dispersion, 324 mg, 8.12 mmol) was added at 0C to a DMF (50 mL) solution of 2,4-dichloropyrimidine (1.0 g, 6.71 mmol) and 2-(3,4-dimethoxyphenyl)ethanol (1.35 g, 7.38 mmol), and the mixture was stirred for 3 hours at 60C. Water was added to the reaction solution, and the product was extracted with ethyl acetate. An ether mixture (1.06 g) was obtained. A 2 N sodium carbonate aqueous solution (20 mL)-1,2-dimethoxyethane (20 mL) mixture of tetrakis(triphenylphosphine)palladium (0) (125 mg, 0.11 mmol), <strong>[4334-87-6](3-(ethoxycarbonyl)phenyl)boronic acid</strong> (837 mg, 4.32 mmol), and the above mixture was reacted for 16 hours at 90C in a nitrogen atmosphere. Water was added to the reaction solution, and the product was extracted with ethyl acetate. The combined organic layers were washed with saturated brine, then dried over anhydrous sodium sulfate, and then concentrated at reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate-hexane 1:1) to give 840 mg (yield: 31%) of ethyl 3-(4-(2-(3,4-dimethoxyphenyl)ethoxy)pyrimidin-2-yl)benzoate and 240 mg (yield: 9%) of ethyl 3-(2-(2-(3,4-dimethoxyphenyl)ethoxy)pyrimidin-4-yl)benzoate.Ethyl 3-(4-(2-(3,4-dimethoxyphenyl)ethoxy)pyrimidin-2-yl)benzoate Melting point: 101 - 102 C. (Ethyl acetate-hexane). 1H-NMR (CDCl3 ) delta : 1.41 (3H, t, J = 7.2 Hz), 3.10 (2H, t, J = 7.2 Hz), 3.86(3H, s), 3.88 (3H, s), 4.42 (2H, q, J = 7.2 Hz), 4.71 (2H, t, J = 7.2 Hz), 6.64 (1H, d, J = 5.4 Hz), 6.79 - 6.90 (3H, m), 7.54 (1H, t, J = 7.5 Hz), 8.15 (1H, d, J = 7.5 Hz), 8.52 (1H, d, J = 5.7 Hz), 8.60 (1H, d, J = 8.1 Hz), 9.07 (1H, s).Ethyl 3-(2-(2-(3,4-dimethoxyphenyl)ethoxy)pyrimidin-4-yl)benzoate Melting point: 94 - 95 C. (Ethyl acetate-hexane). 1H-NMR (CDCl3 ) delta : 1.42 (3H, t, J = 7.2 Hz), 3.14 (2H, t, J = 6.9 Hz), 3.86(3H, s), 3.88 (3H, s), 4.42 (2H, q, J = 7.2 Hz), 4.66 (2H, t, J = 6.9 Hz), 6.79 - 6.90 (3H, m), 7.41 (1H, d, J = 5.1 Hz), 7.56 (1H, t, J = 7.8 Hz), 8.17 (1H, d, J = 7.8 Hz), 8.32 (1H, d, J = 7.8 Hz), 8.57 (1H, d, J = 5.1 Hz), 8.69 (1H, s).

Reference： [1]Patent: EP2253618,2010,A1 .Location in patent: Page/Page column 40

34
[ 1185999-44-3 ]
[ 4334-87-6 ]
[ 1185999-65-8 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 90℃; for 16h;Inert atmosphere;	Reference Example 23; 3-(6-(2-(3,4-dimethoxyphenyl)ethoxy)pyridin-2-yl)benzoic acid; A mixture of 2-chloro-6-(2-(3,4-dimethoxyphenyl)ethoxy)pyridine (1.76 g, 5.99 mmol) obtained in Reference Example 7, <strong>[4334-87-6](3-(ethoxycarbonyl)phenyl)boronic acid</strong> (1.28 g, 6.59 mmol), and tetrakis(triphenylphosphine)palladium (0) (207 mg, 0.18 mmol) in 2 N sodium carbonate aqueous solution (20 mL)-1,2-dimethoxyethane (20 mL) was reacted for 16 hours at 90C in a nitrogen atmosphere. Water was added to the reaction solution, and the product was extracted with ethyl acetate. The combined organic layers were washed with saturated brine, then dried over anhydrous sodium sulfate, and then concentrated at reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate-hexane 2:3) to give 1.36 g of ethyl 3-(6-(2-(3,4-dimethoxyphenyl)ethoxy)pyridin-2-yl)benzoate. 1 N sodium hydroxide aqueous solution (10 mL, 10 mmol) was added at room temperature to an ethanol (50 mL) solution of this compound, and the mixture was stirred for 2 hours at 60C and was then concentrated at reduced pressure. Water and hydrochloric acid were added to the reaction solution to make the aqueous layer acidic, and the product was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off at reduced pressure, and the resulting residue was crystallized from ethyl acetate-hexane to give 820 mg of the titled compound (yield: 36%). Melting point: 147 - 148C. 1H-NMR (CDCl3 ) delta : 3.11 (2H, t, J = 7.2 Hz), 3.86 (3H, s), 3.88 (3H, s), 4.66 (2H, t, J = 7.2 Hz), 6.72 (1H, d, J = 8.1 Hz), 6.82 - 6.91 (3H, m), 7.41 (1H, d, J = 7.5 Hz), 7.57 (1H, t, J = 7.5 Hz), 7.66 (1H, t, J = 7.5 Hz), 8.14 (1H, dd, J = 7.5, 1.2 Hz).8.30 (1H, d, J = 6.6 Hz), 8.76 (1H, s), 1H unconfirmed.
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 90℃; for 16h;Inert atmosphere;	Reference Example 123 3-(6-(2-(3,4-dimethoxyphenyl)ethoxy)pyridin-2-yl)benzoic acid A mixture of 2-chloro-6-(2-(3,4-dimethoxyphenyl)ethoxy)pyridine (1.76 g, 5.99 mmol) obtained in Reference Example 121, <strong>[4334-87-6][3-(ethoxycarbonyl)phenyl]boronic acid</strong> (1.28 g, 6.59 mmol) and tetrakis(triphenylphosphine)palladium(0) (207 mg, 0.18 mmol) in 2 N aqueous sodium carbonate solution (20 mL)-1,2-dimethoxyethane (20 mL) was allowed to react under a nitrogen atmosphere at 90C for 16 hr. Water was added to the reaction mixture and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate-hexane 2:3) to give ethyl 3-(6-(2-(3,4-dimethoxyphenyl)ethoxy)pyridin-2-yl)benzoate (1.36 g). To a solution of the compound in ethanol (50 mL) was added 1 N aqueous sodium hydroxide solution (10 mL, 10 mmol) at room temperature, and the mixture was stirred at 60C for 2 hr and concentrated under reduced pressure. The aqueous layer was acidified with water and hydrochloric acid and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure and the obtained residue was crystallized from ethyl acetate-hexane to give the title compound (820 mg, yield 36%). Melting point 147 - 148C. 1H-NMR (CDCl3) delta : 3.11 (2H, t, J = 7.2 Hz), 3.86 (3H, s), 3.88 (3H, s), 4.66 (2H, t, J = 7.2 Hz), 6.72 (1H, d, J = 8.1 Hz), 6.82-6.91 (3H, m), 7.41 (1H, d, J = 7.5 Hz), 7.57 (1H, t, J = 7.5 Hz), 7.66 (1H, t, J = 7.5 Hz), 8.14 (1H, dd, J = 7.5, 1.2 Hz).8.30 (1H, d, J = 6.6 Hz), 8.76 (1H, s), 1H unconfirmed.

Reference： [1]Patent: EP2253618,2010,A1 .Location in patent: Page/Page column 41
[2]Patent: EP2298731,2011,A1 .Location in patent: Page/Page column 75

35
[ 1185999-99-8 ]
[ 4334-87-6 ]
[ 1186000-01-0 ]

Yield	Reaction Conditions	Operation in experiment
48%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 100℃;Inert atmosphere;	Reference Example 66; Ethyl 3-(6-((2,4-dichlorophenyl)thio)pyridin-2-yl)benzoate; Tetrakis(triphenylphosphine)palladium (0) (802 mg, 0.694 mmol) was added at room temperature in a nitrogen atmosphere to a 1,2-dimethoxyethane (35 mL) solution of2-chloro-6-((2,4-dichlorophenyl)thio)pyridine (1.68 g, 5.78 mmol) obtained in Reference Example 58, (3-(ethoxycarbonyl)-phenyl)boronic acid (1.35 g, 6.94 mmol), and 2 N sodium carbonate aqueous solution (11.6 mL), and the mixture was stirred at 100C over night. Water was poured into the reaction solution, and the product was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous magnesium sulfate, and the solvent was distilled off at reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane = 1:9) to give 1.13 g of the titled compound (yield 48%) in solid form. 1H-NMR (CDCl3 ) delta: 1.36 - 1.46 (3H, m), 4.42 (2H, q, J = 7.2 Hz), 6.91 - 6.99 (1H, m), 7.28 - 7.36 (2H, m), 7.44 - 7.76 (4H, m), 8.01 - 8.14 (2H, m), 8.50 - 8.56 (1H, m).

Reference： [1]Patent: EP2253618,2010,A1 .Location in patent: Page/Page column 49

36
[ 1186000-13-4 ]
[ 4334-87-6 ]
[ 1186000-12-3 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 100℃;Inert atmosphere;	Reference Example 75; Ethyl 3-(6-((2,4-dichlorophenyl)amino)pyridin-2-yl)benzoate; A toluene (20 mL) solution of 2,4-dichloropyridine (1.00 g, 6.71 mmol), 2,4-dichloroaniline (1.20 g, 7.38 mmol), sodium tert-butoxide (968 mg, 10.1 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethyl xanthene (233 mg, 0.403 mmol), and tris(dibenzylideneacetone)dipalladium (0) (123 mg, 0.134 mmol) was stirred at 100C over night. Water was poured into the reaction solution, and the product was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous magnesium sulfate, and the solvent was distilled off at reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane = 1:19) to give 6-chloro-N-(2,4-dichlorophenyl)pyridine-2-amine in the form of a crude product. Tetrakis(triphenylphosphine)palladium (0) (862 mg, 0.746 mmol) was added at room temperature in a nitrogen atmosphere to a 1,2-dimethoxyethane (35 mL) solution of the above compound (1.71 g), (3-(ethoxycarbonyl)-phenyl)boronic acid (1.33 g, 6.84 mmol), and 2 N sodium carbonate aqueous solution (12.4 mL), and the mixture was stirred at 100C over night. Water was poured into the reaction solution, and the product was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous magnesium sulfate, and the solvent was distilled off at reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane = 1:9) to give 1.41 g of the titled compound (yield 54%) in solid form. 1H-NMR (CDCl3 ) delta: 1.44 (3H, t, J = 7.2 Hz), 4.43 (2H, q, J = 7.2 Hz), 6.78 (1H, d, J = 8.1 Hz), 6.92 (1H, s), 7.24 - 7.31 (1H, m), 7.34 - 7.43 (2H, m), 7.51 - 7.58 (1H, m), 7.66 (1H, t, J = 8.1 Hz), 8.05 - 8.12 (1H, m), 8.18 - 8.24 (1H, m), 8.39 (1H, t, J = 8.1 Hz), 8.67 (1H, t, J = 1.7 Hz).

Reference： [1]Patent: EP2253618,2010,A1 .Location in patent: Page/Page column 51

37
[ 1186000-15-6 ]
[ 4334-87-6 ]
[ 1186000-14-5 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 100℃;Inert atmosphere;	Reference Example 76; Ethyl 3-(6-(2,4-dichlorophenoxy)-3-(trifluoromethyl)pyridin-2-yl)benzoate; A DMF (15 mL) solution of 2,6-dichloro-3-(trifluoromethyl)pyridine (1.00 g, 4.63 mmol), 2,4-dichlorophenol (792 mg, 4.86 mmol), and potassium carbonate (704 mg, 5.09 mmol) was stirred at 120C for 3 hours. Water was poured into the reaction solution, and the product was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous magnesium sulfate, and the solvent was distilled off at reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane = 1:99) to give 2-chloro-6-(2,4-dichlorophenoxy)-3-(trifluoromethyl)pyridine in the form of a crude product. Tetrakis(triphenylphosphine)palladium (0) (474 mg, 0.410 mmol) was added at room temperature in a nitrogen atmosphere to a 1,2-dimethoxyethane (20 mL) solution of the above compound (1.17 g), (3-(ethoxycarbonyl)-phenyl)boronic acid (729 mg, 3.76 mmol), and 2 N sodium carbonate aqueous solution (6.8 mL), and the mixture was stirred at 100C over night. Water was poured into the reaction solution, and the product was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous magnesium sulfate, and the solvent was distilled off at reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane = 1:19) to give 788 mg of the titled compound (yield 51%) in the form of an oily substance. 1H-NMR (CDCl3 ) delta: 1.39 (3H, t, J = 7.1 Hz), 4.28 (2H, q, J = 7.1 Hz), 7.04 (1H, d, J = 8.5 Hz), 7.14 - 7.20 (1H, m), 7.22 - 7.29 (1H, m), 7.41 - 7.50 (2H, m), 7.56 - 7.64 (1H, m), 8.04 - 8.14 (3H, m).

Reference： [1]Patent: EP2253618,2010,A1 .Location in patent: Page/Page column 51

38
[ 4548-45-2 ]
[ 4334-87-6 ]
[ 1258391-89-7 ]

Yield	Reaction Conditions	Operation in experiment
89%	With sodium carbonate; tert-butyl XPhos;bis-triphenylphosphine-palladium(II) chloride; In 1,4-dioxane; water; at 90℃; for 10h;Inert atmosphere;	To a solution of 2-chloro-5-nitropyridine (5.23 g, 32.99 mmol) in dioxane (170 mL) was added 3-(ethoxycarbonyl)phenylboronic acid (6.28 g, 32.99 mmol) and IN Na2CO3 aqueous solution (82.5 mL, 82.5 mmol). The reaction mixture was degassed using Argon gas for 20 min followed by the addition of dichlorobis(triphenylphospine)palladium(II) (1.38 g, 1.99 mmol) and 2-di-tert- butylphosphino-2',4',6'-triisopropylbiphenyl (1.26 g, 2.97 mmol). The reaction flask was put into the preheated oil-bath at 90 0C. The reaction mixture was further stirred at 90 0C for a period of 10 h after which it was filtered and partitioned between ethyl acetate and water. The organic layer was separated and the aqueous layer was extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over MgSO4, filtered and concentrated. The crude product was purified by flash column chromatography using a 95:5 v/v hexane:ethyl acetate as solvent to afford ethyl 3-(5- nitropyridin-2-yl)benzoate (8.0 g, 89% yield) as a bright yellow solid. 1H NMR 600 MHz (CDCl5) delta 9.50 (s, IH), 8.71 (s, IH), 8.55 (J, J= 7.8 Hz, IH), 8.32 (J, J = 7.2 Hz, IH), 8.18 (J, J = 7.2 Hz, IH), 7.98 (J, J = 8.4 Hz, IH), 7.61 (t, J = 7.2 Hz, IH), 4.43 (q, 2H), 1.43 (f, 3H), MS m/z : 273.22 (M + 1).

Reference： [1]Patent: WO2010/144909,2010,A1 .Location in patent: Page/Page column 71-72
[2]Bioorganic and Medicinal Chemistry Letters,2012,vol. 22,p. 5297 - 5302

39
[ 4334-87-6 ]
[ 6945-68-2 ]
[ 1258391-99-9 ]

Yield	Reaction Conditions	Operation in experiment
78%	With sodium carbonate; tert-butyl XPhos;bis-triphenylphosphine-palladium(II) chloride; In 1,4-dioxane; water; at 90℃; for 10h;Inert atmosphere;	To a solution of <strong>[6945-68-2]5-bromo-3-nitropyridin-2-amine</strong> (5.00 g, 23.97 mmol) in dioxane (115 niL) was added 3-(ethoxycarbonyl)phenylboronic acid (4.65 g, 23.97 mmol) and INNa2CO3 aqueous solution (92.2 mL, 92.2 mmol). The reaction mixture was degassed using Argon gas for 20 min followed by the addition of dichlorobis(triphenylpho spine) palladium(II) (971 mg, 1.38 mmol) and 2-di-tert- butylphosphino-2',4',6'-triisopropylbiphenyl (881 mg, 2.07 mmol). The reaction flask was put into the preheated oil-bath at 90 0C. The reaction mixture was further stirred at 90 0C for a period of 10 h after which it was filtered and partitioned between ethyl acetate and water. The organic layer was separated and the aqueous layer was extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over MgSO4, filtered and concentrated. The crude product was purified by flash column chromatography using a 90:10 v/v hexane:ethyl acetate as solvent to afford ethyl 3-(6- amino-5-nitropyridin-3-yl)benzoate (5.2 g, 78% yield) as a tan solid. MS m/z : 288.23 (M + 1).

Reference： [1]Patent: WO2010/144909,2010,A1 .Location in patent: Page/Page column 79

40
[ 1150617-92-7 ]
[ 4334-87-6 ]
[ 1202504-48-0 ]

Yield	Reaction Conditions	Operation in experiment
23%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 90℃; for 48h;Inert atmosphere;	Reference Example 105 ethyl 3-(7-oxo-6,7-dihydro-5H-cyclopenta[b]pyridin-2-yl)benzoate A mixture of 2-chloro-5,6-dihydro-7H-cyclopenta[b]pyridin-7-one (2.83 g, 16.9 mmol) obtained in Reference Example 104, <strong>[4334-87-6][3-(ethoxycarbonyl)phenyl]boronic acid</strong> (4.91 g, 25.3 mmol), sodium carbonate (3.58 g, 33.8 mmol) and tetrakis(triphenylphosphine)palladium(0) (1.74 g, 1.69 mmol) in water (10 mL)-toluene (40 mL)-ethanol (20 mL) was reacted under a nitrogen atmosphere at 90C for 2 days. Water was added to the reaction mixture, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane-ethyl acetate 8:1) to give the title compound (1.10 g, yield 23%) as crystals. 1H-NMR (CDCl3) delta : 1.43 (3H, t, J = 7.2 Hz), 2.83 - 2.86 (2H, m), 3.21 - 3.24 (2H, m), 4.43 (2H, q, J = 7.2 Hz), 7.58 (1H, t, J = 7.6 Hz), 7.99 (2H, s), 8.13 (1H, ddd, J = 7.7, 1.6, 1.6 Hz), 8.40 (1H, ddd, J = 4.8, 2.0, 1.2 Hz), 8.64 (1H, dd, J = 1.4, 1.4 Hz).

Reference： [1]Patent: EP2298731,2011,A1 .Location in patent: Page/Page column 71

41
[ 1202502-83-7 ]
[ 4334-87-6 ]
[ 1202502-85-9 ]

Yield	Reaction Conditions	Operation in experiment
74%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 90℃;Inert atmosphere;	Reference Example 30 ethyl 3-[1-[2-(3,4-dimethoxyphenyl)ethyl]-1H-pyrrolo[2,3-b]pyridin-6-yl]benzoate A mixture of 6-chloro-1-[2-(3,4-dimethoxyphenyl)ethyl]-1H-pyrrolo[2,3-b]pyridine (600 mg, 1.89 mmol) obtained in Reference Example 29, <strong>[4334-87-6][3-(ethoxycarbonyl)phenyl]boronic acid</strong> (441 mg, 2.27 mmol) and tetrakis(triphenylphosphine)palladium(O) (263 mg, 0.227 mmol) in 2 N aqueous sodium carbonate solution (3.8 ml)-1,2-dimethoxyethane (18 ml) was stirred overnight under a nitrogen atmosphere at 90C. Water was poured into the reaction mixture and the mixture was extracted with ethyl acetate. The extract was washed with water, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane = 1:9) to give the title compound (606 mg, yield 74%) as an oil. 1H-NMR (CDCl3) delta: 1.44 (3H, t, J = 7.1 Hz), 3.17 (2H, t, J = 7.1 Hz), 3.71 (3H, s), 3.82 (3H, s), 4.44 (2H, q, J = 7.1 Hz), 4.59 (2H, t, J = 7.1 Hz), 6.39 (1H, d, J = 3.4 Hz), 6.47 - 6.52 (1H, m), 6.68 - 6.81 (2H, m), 7.02 (1H, d, J = 3.4 Hz), 7.55 (1H, t, J = 7.8 Hz), 7.61 (1H, d, J = 8.3 Hz), 7.96 (1H, d, J = 8.3 Hz), 8.02 - 8.08 (1H, m), 8.32 - 8.38 (1H, m), 8.77 (1H, t, J = 1.5 Hz).

Reference： [1]Patent: EP2298731,2011,A1 .Location in patent: Page/Page column 55

42
[ 1202503-19-2 ]
[ 4334-87-6 ]
[ 1202503-15-8 ]

Yield	Reaction Conditions	Operation in experiment
64%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 20 - 100℃;Inert atmosphere;	Reference Example 44 ethyl 3-[1-(2,4-dichlorophenyl)-1H-pyrazolo[3,4-b]pyridin-6-yl]benzoate A mixture of 2,6-dichloropyridine-3-carbaldehyde (800 mg, 4.55 mmol), 2,4-dichlorophenylhydrazine hydrochloride (1.07 g, 5.00 mmol) and ethanol (16 ml) was stirred at 90C for 3 hr, and the reaction solution was concentrated. Diethyl ether was added to the residue and 2,6-dichloro-3-[(E)-[(2,4-dichlorophenyl)hydrazono]methyl]pyridine (1.49 g, yield 98%) was collected by filtration to give a solid. A mixture of the compound (1.49 g), sodium tert-butoxide (641 mg, 6.67 mmol), tris(dibenzylideneacetone)dipalladium(O) (81.5 mg, 0.089 mmol), 2-(dicyclohexylphosphino)-2',4',6'-triisopropyl-1,1'-biphenyl (127 mg, 0.267 mmol) and 1,4-dioxane (20 ml) was stirred in a microwave reactor (Initiator (trade name), Biotage AB) at 120C for 30 min. Water was poured into the reaction solution and the mixture was extracted with ethyl acetate. The extract was washed with water, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane = 1:19) to give 6-chloro-1-(2,4-dichlorophenyl)-1H-pyrazolo[3,4-b]pyridine (339 mg, yield 26%) as a solid. To a solution of the compound (365 mg), <strong>[4334-87-6][3-(ethoxycarbonyl)-phenyl]boronic acid</strong> (261 mg, 1.34 mmol) and 2 N aqueous sodium carbonate solution (2.4 ml) in 1,2-dimethoxyethane (12 ml) was added under a nitrogen atmosphere tetrakis(triphenylphosphine)palladium(O) (170 mg, 0.147 mmol) at room temperature, and the mixture was stirred overnight at 100C. Water was poured into the reaction mixture and the mixture was extracted with ethyl acetate. The extract was washed with water, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane= 1:9) to give the title compound (321 mg, yield 64%) as an oil. 1H-NMR (CDCl3) delta: 1.43 (3H, t, J = 7.2 Hz), 4.36 - 4.46 (2H, m), 7.44 (1H, dd, J = 8.6, 2.4 Hz), 7.51 - 7.62 (2H, m), 7.66 (1H, d, J = 2.4 Hz), 7.78 (1H, d, J = 8.6 Hz), 8.10 (1H, dd, J = 7.7, 1.1 Hz), 8.17 - 8.34 (3H, m), 8.70 (1H, s).

Reference： [1]Patent: EP2298731,2011,A1 .Location in patent: Page/Page column 58

43
[ 1202503-42-1 ]
[ 4334-87-6 ]
[ 1202503-49-8 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 90℃; for 16h;Inert atmosphere;	Reference Example 56 3-[3-(2,4-dichlorobenzyl)-3H-imidazo[4,5-b]pyridin-5-yl]benzoic acid A mixture of 5-chloro-3-(2,4-dichlorobenzyl)-3H-imidazo[4,5-b]pyridine (3.6 g, 11.5 mmol) obtained in Reference Example 55, <strong>[4334-87-6][3-(ethoxycarbonyl)phenyl]boronic acid</strong> (2.67 g, 13.8 mmol) and tetrakis(triphenylphosphine)palladium(0) (664 mg, 0.58 mmol) in 2 N aqueous sodium carbonate solution (30 mL)-1,2-dimethoxyethane (30 mL) was reacted under a nitrogen atmosphere at 90C for 16 hr. Water was added to the reaction mixture and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate-hexane 2:3) to give ethyl 3-[3-(2,4-dichlorobenzyl)-3H-imidazo[4,5-b]pyridin-5-yl]benzoate (1.72 g). To a solution of the compound in ethanol (50 mL) was added 1 N aqueous sodium hydroxide solution (10 mL, 10 mmol) at room temperature, and the mixture was stirred at 60C for 2 hr, and concentrated under reduced pressure. Water and hydrochloric acid were added to the reaction mixture to acidify the aqueous layer, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure and the obtained residue was crystallized from ethyl acetate-hexane to give the title compound (1.1 g, yield 24%). Melting point 258 - 260C. 1H-NMR (DMSO-d6) delta: 5.77 (2H, s), 6.60 (1H, brs), 7.47 (1H, dd, J = 8.1, 2.1 Hz), 7.56 - 7.72 (3H, m), 8.02 (1H, d, J = 7.8 Hz), 8.12 (1H, d, J = 8.4 Hz), 8.30 - 8.37 (2H, m), 8.70 (1H, s), 9.28 (1H, s).

Reference： [1]Patent: EP2298731,2011,A1 .Location in patent: Page/Page column 60-61

44
[ 1217340-49-2 ]
[ 4334-87-6 ]
[ 1217339-20-2 ]

Yield	Reaction Conditions	Operation in experiment
85%	With caesium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 90℃;	Cesium carbonate (1.69 g, 5.19 mmol) was added to Pd(Ph3P)4 (250 mg, 0.216 mmol), 2-(4-fluorophenyl)-3-(methylcarbamoyl)-6-nitrobenzofuran-5-yl trifluoromethanesulfonate (2.00 g, 4.33 mmol), 3-(ethoxycarbonyl)phenylboronic acid (1.01 g, 5.19 mmol). Dioxane (36 mL) and water (7 mL) was added at rt and the mixture was degassed 3x. The reaction was heated to 90 C overnight. It was allowed to cool. The mixture was diluted with EtOAc and washed with 1M HCl, and sat NaCl. The organic phase was dried over Na2S04, filt and concentrated. The crude solid was triturated with DCM to give the titled compound (1.70 g, 85%). 1H NMR (400 MHz, DMSO-d6) deltadelta ppm 8.55 - 8.61 (1 H, m), 8.54 (1 H, s), 8.00 - 8.09 (3 H, m), 7.95 (1 H, s), 7.73 (1 H, s), 7.61 - 7.70 (2 H, m), 7.45 (2 H, t, J=8.91 Hz), 4.35 (2 H, q, J=7.19 Hz), 2.83 (3 H, d, J=4.52 Hz), 1.34 (3 H, t, J=7.03 Hz). LC-MS retention time: 1.62 min; m/z (MH+): 463. LC data was recorded on a Shimadzu LC-10AS liquid chromatograph equipped with a Waters XBridge 5u C18 4.6x50mm column using a SPD-10AV UV-Vis detector at a detector wave length of 220nM. The elution conditions employed a flow rate of 5 ml/min , a gradient of 100% solvent A / 0% solvent B to 0% solvent A / 100% solvent B, a gradient time of 2 min, a hold time of 1 min, and an analysis time of 3 min where solvent A was 5% acetonitrile / 95% H20 / 10 mM ammonium acetate and solvent B was 5% H20 / 95% acetonitrile / 10 mM ammonium acetate. MS data was determined using a Micromass Platform for LC in electrospray mode.

Reference： [1]Patent: WO2011/112191,2011,A1 .Location in patent: Page/Page column 181

45
[ 1217339-11-1 ]
[ 4334-87-6 ]
C₂₄H₁₉FN₂O₆S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		DIEA (134 muIota_,, 0.765 mmol) was added to Pd(Ph3P)4 (30 mg, 0.025 mmol), 2-(4-fluorophenyl)-3- (methylcarbamoyl)-6-(N-(methylsulfonyl)methylsulfonamido)benzofuran-5-yl trifluoromethanesulfonate (150 mg, 0.255 mmol), 3-(ethoxycarbonyl)phenylboronic acid (74 mg, 0.382 mmol). Dioxane (5 mL) and water (1 mL) was added at rt. The reaction was degassed 3x and heated to 90 C overnight. It was allowed to cool and left to stir for 3 days at rt. Step 2: The mixture was concentrated and diluted with EtOH (5 mL) and treated with excess IN NaOH (~1 mL) and allowed to stir at rt overnight to give the meta-acid. The mixture was diluted with EtOAc and washed with 1M HC1, and 1M HC1. The organic phase was dried over Na2S04, filtered and concentrated.

Reference： [1]Patent: WO2011/112191,2011,A1 .Location in patent: Page/Page column 202

46
[ 404827-77-6 ]
[ 4334-87-6 ]
[ 1334419-92-9 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; water; at 100℃; for 4h;	To a solution of 6-bromo- l H-indazol-3-amine (2. 1 g, 10.0 mmol) in dioxane ( 100 mL) and sodium carbonate ( I , 40 mL) were added 3-(ethoxycarbonyl)phenylboronic acid ( 1.94 g, 10.0 mmol) and Pd(dppf)Cl2 (816 mg, 1.0 mmol). After the reaction was stirred at 1 00 C for 4 hours and cooled to room temperature, the mixture was filtered through Celite and washed by ethyl acetate. The combined organic solution was washed by brine, dried with sodium sulfate and concentrated in vacuo. The crude residue was purified by flash chromatography with 50: 1 (v/v) methylene chloride - methanol to afford the title product ( 1 .46 g), MS m/z : 282. 1 1 (M + 1 )

Reference： [1]Patent: WO2011/115725,2011,A2 .Location in patent: Page/Page column 57

47
[ 1334419-88-3 ]
[ 4334-87-6 ]
[ 1334419-89-4 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; water; at 100℃; for 4h;	To a solution of N-(6-bromo- l H-indazol-3-yl)cyclopropanecarboxamide (560 mg, 2.0 mmol) in dioxane (20 mL) and 1 N sodium carbonate solution (8 mL) were added 3- (ethoxycarbonyl)phenylboronic acid (388 mg, 2.0 mmol) and Pd(dppf)Cl2 ( 103 mg, 0.2 mmol). After the reaction was stirred at 100 C for 4 hours and cooled to room temperature, the mixture was filtered through Celite and washed by ethyl acetate. The combined organic solution was washed by brine, dried with sodium sulfate and concentrated in vacuo. The crude residue was purified by flash chromatography with 20: 1 (v/v) methylene chloride - methanol to afford the title product (560 mg). NMR 600 MHz (DMSO-d6) delta 12.70 (s, I H), 10.69 (s, I H), 8.21 (s, I H), 7.99 (d, 7.8 Hz, I H), 7.96 (d, 7.8 Hz, I H), 7.88 (d, 8.4 Hz, I H), 7.63 (m, 2H), 7.34 (d, 8.4 Hz, I H), 4.35 (q, 7.2 Hz, 2H), 1.94 (m, I H), 1.34 (t, 7.2 Hz, 3H), 0.8 - 0.9 (m, 4H). MS m/z : 350. 14 (M + l )

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2012,vol. 22,p. 4579 - 4584
[2]Patent: WO2011/115725,2011,A2 .Location in patent: Page/Page column 51; 52; 53

48
[ 1352005-43-6 ]
[ 4334-87-6 ]
[ 1352005-44-7 ]

Yield	Reaction Conditions	Operation in experiment
34%	With caesium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; at 90℃; for 18h;Inert atmosphere;	PREPARATION 9 Ethyl 3'-(1-ethyl-6-oxo-5-(quinolin-5-ylamino)-1 ,6-dihydropyridazin-3-yl)biphenyl-3-carboxylate In a Schlenk tube, a mixture of 6-(3-bromophenyl)- 2-ethyl-4- (quinolin-5-ylamino) pyridazin-3(2H)-one (3.48g, 8.26 mmol), 3-(ethoxycarbonyl)phenylboronic acid (2.7 g, 13.92 mmol) and cessium carbonate (13.60 g, 3.29 mmol) was dissolved in dioxane (80ml). The mixture was purged (vacuum-argon three times) and [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II)dichloromethanecomplex(0.41g, 0.51 mmol) was added. The mixture was purged again (vacuum-argon three times) and stirred at 90 C for 18 h. The suspension was filtered off and the filtrated diluted with water and extracted three times with ethyl acetate. The combined organic layers were washed with water and brine, and dried over anhydrous sodium sulphate. Solvent was removed in vacuum and the residue was purified by the SP1 automated purification system to give 1.36g (34%) of the desired compound. HPLC/MS (9 min) retention time 7.52 min. LRMS: m/z 491 (M+H+)

Reference： [1]Patent: EP2394998,2011,A1 .Location in patent: Page/Page column 17-18

49
[ 1352005-48-1 ]
[ 4334-87-6 ]
[ 1352005-46-9 ]

Yield	Reaction Conditions	Operation in experiment
38%	With caesium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; at 90℃; for 18h;Inert atmosphere;	PREPARATION 11 Ethyl 3'-(1-ethyl-5-(isoquinolin-4-ylamino)-6-oxo-1,6-dihydropyridazin-3-yl)biphenyl-3-carboxylate In a Schlenk tube, a mixture of 6-(3-bromophenyl)-2-ethyl-4-(quinolin-4-ylamino)pyridazin-3(2H)-one (640 mg, 1.23 mmol, see Preparation 10), 3-(ethoxycarbonyl)phenylboronic acid (320 mg, 1.65 mmol) and cessium carbonate (1.2 g, 3.74 mmol) was dissolved in dioxane (6 mL). The mixture was purged (vacuum-argon three times) and [1,1-bis (diphenylphosphino) ferrocene] dichloropalladium (II) dichloromethane complex (65 mg, 0.08 mmol) was added. The mixture was purged again (vacuum-argon three times) and stirred at 90 C for 18 h. The suspension was filtered off and the filtrated diluted with water and extracted three times with ethyl acetate. The combined organic layers were washed with water and brine, and dried over anhydrous sodium sulphate. Solvent was removed in vacuum and the residue was soaked with ethyl ether and subsequently filtered to give 0.29 g (38%) of the desired compound. HPLC/MS (9 min) retention time 7.55 min. LRMS: m/z 604 (M+H+)

Reference： [1]Patent: EP2394998,2011,A1 .Location in patent: Page/Page column 18-19

50
[ 4334-87-6 ]
[ 77152-08-0 ]
[ 76783-59-0 ]

Reference： [1]Angewandte Chemie - International Edition,2012,vol. 51,p. 7767 - 7770

51
[ 1111638-42-6 ]
[ 4334-87-6 ]
[ 1401732-54-4 ]

Yield	Reaction Conditions	Operation in experiment
	With caesium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; at 100℃; for 16.5h;Inert atmosphere; Sealed tube;	EXAMPLE 82: ethyl 3 -(l-(4-methoxybenzyl -3 -methyl- lH-pyrazoloB.4-b1pyridin-5- vDbenzoateTo a stirred solution of 5-bromo-l-(4-methoxybenzyl)-3-methyl-lH-pyrazolo[3,4-b]pyridine (7) (171 mg, 0.515 mmol, 1 eq) and <strong>[4334-87-6](3-(ethoxycarbonyl)phenyl)boronic acid</strong> (100 mg, 0.515 mmol, 1 eq) in 1 ,2-dimethoxyethane (6 mL) was added CS2CO3 (335 mg, 1.03 mmol, 2.0 eq). The reaction mixture was degassed and purged under N2 for 15 min and Pd(PPh3)4 (0.0238 mg, 0.0206, 0.04 eq)was added and the reaction mixture again purged under N2 for another 15 min. The reaction mixture was heated at 100C in a sealed tube for 16 hrs. After completion, the reaction was partitioned between ethyl acetate/water; the organic layer was separated and extracted again into ethyl acetate. The combined organic layer was dried over sodium sulphate and the solvents were removed to get the crude product. The crude material was flashed through 100-200 mesh silica gel eluting the pure compound in 25% EtOAc/Hexane as off-white coloured solid ethyl 3-(l-(4-methoxybenzyl)-3-methyl-lH-pyrazolo[3,4-b]pyridin-5-yl)benzoate 118 (70 mg).

Reference： [1]Patent: WO2012/135631,2012,A1 .Location in patent: Page/Page column 62-63

52
[ 943722-20-1 ]
[ 4334-87-6 ]
[ 1412438-59-5 ]

Yield	Reaction Conditions	Operation in experiment
60%	With caesium carbonate;dichloro[1,1'-bis(di-t-butylphosphino)ferrocene]palladium(II); In 1,4-dioxane; at 100℃;Inert atmosphere;	Intermediate 7: Ethyl 3-[3-(aminomethyl)-2-methylphenyll-benzoate:To a solution of intermediate 3 (15 g, 75 mmol, 1.0 eq), 3-(ethoxycarbonyl)phenyl)boronic acid (21 .8 g, 1 12.5 mmol, 1.5 eq) and Cs2C03 (36.6 g, 1 12.5 mmol, 1.5 eq) in dioxane (300 ml) was added PdCI2(dtbpf) (0.964 g, 3.75 mmol, 0.05 eq) under N2 protection. The reaction mixture was heated to 100 C with stirring overnight and then cooled to room temperature. The solvent was evaporated by rotavapor and EtOAc (400 ml) was added into the mixture. After washing with H20 (200 ml x3), drying over MgS04, filtration and evaporation under reduced pressure, the residue was dissolved in EtOAc (300 ml). Then 10% aq. HCI (15 ml) was added dropwise and the resulting precipitate was filtered and dried to give intermediate 7 (12 g, 60% yield) as a white solid.

Reference： [1]Patent: WO2012/156467,2012,A1 .Location in patent: Page/Page column 48

53
[ 20358-03-6 ]
[ 4334-87-6 ]
[ 1415695-82-7 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2012,vol. 22,p. 7719 - 7725

54
[ 4334-87-6 ]
[ 938-40-9 ]
4-(3-ethoxycarbonylphenyl)-2H-benzopyran-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With sodium carbonate; In tetrahydrofuran; for 3h;Reflux;	4.5.1 4-(3-Ethoxycarbonylphenyl)-2H-benzopyran-2-one 4g In a 30 mL Schlenk tube equipped with a magnetic stirring bar, complex 1 (5.0 mol %), 4-bromocoumarin (1 mmol) were taken in THF (2 mL) and Na2CO3 solution (2.0 M, 1 mL). The solutions were degassed (three freeze-thaw cycles) and stirred for 10 min. After this time period, to the solution 3-ethoxycarbonylphenyl boronic acid (1 mmol) was added and the mixtures degassed. The reaction mixtures were refluxed for 3.0 h. The reactions were monitored by TLC. The reaction mixtures were then evaporated in vacuo. The resultant residues were purified by flash chromatography (silica gel) to afford the desired product as a colourless solid. Rf 0.34 (E.A 10%/PE 90%); 249 mg, 85%. Mp 123-124 C; IR (KBr, cm-1): 3054, 1726, 1702, 1608, 1302, 1166, 1030, 747; 1H NMR (300 MHz, DMSO-d6) delta=8.12-8.16 (m, 1H, Ar-H), 8.05 (s, 1H, Ar-H), 7.43-7.54 (m, 2H, Ar-H), 7.31-7.38 (m, 2H, Ar-H), 7.15-7.26 (m, 2H, Ar-H), 6.34 (s, 1H, CH), 4.32 (q, J=7.4 Hz, 2H, OCH2), 1.34 (t, J=7.6 Hz, 3H, CH3); 13C NMR (75 MHz, DMSO-d6) delta=165.9 (Cq), 160.6 (Cq), 154.8 (Cq), 154.2 (Cq), 135.4 (Cq), 132.6 (CH), 132.2 (CH), 131.3 (Cq), 130.7 (CH), 129.5 (CH), 129.4 (CH), 126.7 (CH), 124.4 (CH), 118.8 (Cq), 117.5 (CH), 115.6 (CH), 61.5 (OCH2), 14.3 (CH3). MS (ESI) m/z (relative intensity) 295 (100, M+H+); HRMS (ESI, quadrapole): m/z calcd for C18H14O4+H+ 295.0970; found 295.0968. Anal. Calcd for C18H14O4: C, 73.46; H, 4.79. Found: C, 73.45; H, 4.80%.

Reference： [1]Tetrahedron,2013,vol. 69,p. 1446 - 1453

55
[ 4334-87-6 ]
[ 132559-91-2 ]
[ 1421194-13-9 ]

Yield	Reaction Conditions	Operation in experiment
80%	With sodium carbonate; In tetrahydrofuran; for 3h;Reflux;	4.5.3 4-(3-Ethoxycarbonylphenyl)-6-methyl-2-pyranone 6e In a 30 mL Schlenk tube equipped with a magnetic stirring bar, complex 1 (5.0 mol %), 4-bromo-6-methyl-2-pyranone (1 mmol) were taken in THF (2 mL) and Na2CO3 solution (2.0 M, 1 mL). The solutions were degassed (three freeze-thaw cycles) and stirred for 10 min. After this time period, to the solution 3-ethoxycarbonylphenyl boronic acid (1 mmol) was added and the mixtures degassed. The reaction mixtures were refluxed for 3.0 h. The reactions were monitored by TLC. The reaction mixtures were then evaporated in vacuo. The resultant residues were purified by flash chromatography (silica gel) to afford the desired product as a colourless solid. Rf 0.36 (E.A 10%/PE 90%). Mp 148-150 C; IR (KBr, cm-1): 3048, 1731, 1706, 1621, 1304, 1173, 1050, 747; 1H NMR (300 MHz, DMSO-d6) delta=8.25 (s, 1H, Ar-H), 8.05-8.14 (m, 1H, Ar-H), 7.67-7.73 (m, 1H, Ar-H), 7.43-7.48 (m, 1H, Ar-H), 6.75 (s, 1H, CH), 6.64 (s, 1H, CH), 4.32 (q, J=7.5 Hz, 2H, OCH2), 2.34 (s, 3H, CH3), 1.34 (t, J=7.5 Hz, 3H, CH3); 13C NMR (75 MHz, DMSO-d6) delta=165.1 (Cq), 162.7 (Cq), 162.1 (Cq), 153.6 (Cq), 135.5 (Cq), 131.5 (CH), 131.0 (CH), 130.8 (CH), 129.7 (CH), 127.1 (CH), 107.7 (CH), 102.7 (CH), 61.0 (OCH2), 19.5 (CH3), 14.1 (CH3); MS (ESI) m/z (relative intensity) 259 (100, M+H+); HRMS (ESI, quadrapole): m/z calcd for C15H15O4 259.0970; found 259.0969. Anal. Calcd for C15H15O4: C, 69.76; H, 5.46. Found: C, 69.77; H, 5.46%.

Reference： [1]Tetrahedron,2013,vol. 69,p. 1446 - 1453

56
[ 38267-96-8 ]
[ 4334-87-6 ]
[ 1431542-29-8 ]

Yield	Reaction Conditions	Operation in experiment
2.12 g	With bis-triphenylphosphine-palladium(II) chloride; potassium phosphate; In water; acetonitrile; at 100℃; for 0.25h;Microwave irradiation;	To a mixture of 6-Bromo-4-chloro-quinazoline (2g, 8.21 mmol), 3-(ethoxycarbonyl)phenyl- boronic acid (1 .673g, 8.62 mmol), Pd(PPh3)2CI2 (0.288g, 0.41 1 mmol) and K3P04 (2.62g, 12.32 mmol) was added 16 mL of acetonitrile. The reaction mixture was flushed with argon, 2mL of water was added, the tube was capped, heated to 100C for 15min using a microwave oven and then cooled down to rt. The formed yellow solid was filtered, washed with ether and dried under vacuum to gave the title compound (1.54g) as a yellow solid. The filtrate was diluted with EtOAc, the organic layer washed with brine, dried over MgS04, filtered and evaporated. The obtained residue was triturated in MeOH to afford the title compound as a yellow solid (580 mg). The two solids were combined to gave 2.12g of the title compound as a yellow solid. 1H-NMR (400 MHz, MeOD, 298 K): ? ppm 1 .42 (t, 3 H) 4.43 (q, 2 H) 7.77 (t, 1 H) 7.97-8.07 (m, 2 H) 8.16 (dd, 1 H) 8.22 (d, 1 H) 8.29 (d, 1 H) 8.41 (s, 1 H) 9.34 (s, 1 H). MS: 357.0-359.0 [M+1 ]+, Rt (1) = 1 .52 min.
2.12 g	With bis-triphenylphosphine-palladium(II) chloride; potassium acetate; In water; acetonitrile; at 100℃; for 0.25h;Inert atmosphere; Microwave irradiation;	To a mixture of 6-Bromo-4-chloro-quinazoline (2g, 8.21 mmol), 3-(ethoxycarbonyl)phenyl- boronic acid (1.673g, 8.62 mmol), Pd(PPh3)2Cl2 (0.288g, 0.41 1 mmol) and K3P04 (2.62g, 12.32 mmol) was added 16 mL of acetonitrile. The reaction mixture was flushed with argon, 2ml_ of water was added, the tube was capped, heated to 100C for 15min using a microwave oven and then cooled down to rt. The formed yellow solid was filtered, washed with ether and dried under vacuum to gave the title compound (1.54g) as a yellow solid. The filtrate was diluted with EtOAc, the organic layer washed with brine, dried over MgS04, filtered and evaporated. The obtained residue was triturated in MeOH to afford the title compound as a yellow solid (580 mg). The two solids were combined to gave 2.12g of the title compound as a yellow solid. 1H-NMR (400 MHz, MeOD 298 K): delta ppm 1.42 (t, 3 H) 4.43 (q, 2 H) 7.77 (t, 1 H) 7.97-8.07 (m, 2 H) 8.16 (dd, 1 H) 8.22 (d, 1 H) 8.29 (d, 1 H) 8.41 (s, 1 H) 9.34 (s, 1 H). MS: 357.0-359.0 [M+1]+, Rt = 1.52 min.
2.12 g	With bis-triphenylphosphine-palladium(II) chloride; potassium phosphate; In water; acetonitrile; at 100℃; for 0.25h;Inert atmosphere; Microwave irradiation;	3-(6-Bromo-quinazolin-4-yl)-benzoic acid ethyl ester To a mixture of 6-Bromo-4-chloro-quinazoline (2 g, 8.21 mmol), 3-(ethoxycarbonyl)phenyl-boronic acid (1.673 g, 8.62 mmol), Pd(PPh3)2Cl2 (0.288 g, 0.411 mmol) and K3PO4 (2.62 g, 12.32 mmol) was added 16 mL of acetonitrile. The reaction mixture was flushed with argon, 2 mL of water was added, the tube was capped, heated to 100 C. for 15 min using a microwave oven and then cooled down to rt. The formed yellow solid was filtered, washed with ether and dried under vacuum to gave the title compound (1.54 g) as a yellow solid. The filtrate was diluted with EtOAc, the organic layer washed with brine, dried over MgSO4, filtered and evaporated. The obtained residue was triturated in MeOH to afford the title compound as a yellow solid (580 mg). The two solids were combined to gave 2.12 g of the title compound as a yellow solid. 1H-NMR (400 MHz, MeOD, 298 K): delta ppm 1.42 (t, 3H) 4.43 (q, 2H) 7.77 (t, 1H) 7.97-8.07 (m, 2H) 8.16 (dd, 1H) 8.22 (d, 1H) 8.29 (d, 1H) 8.41 (s, 1H) 9.34 (s, 1H). MS: 357.0-359.0 [M+1]+, Rt(1')=1.52 min.

Reference： [1]ACS Medicinal Chemistry Letters,2016,vol. 7,p. 762 - 767
[2]Patent: WO2013/57711,2013,A1 .Location in patent: Page/Page column 56-57
[3]Patent: WO2013/88404,2013,A1 .Location in patent: Page/Page column 185; 186
[4]Patent: US2015/342951,2015,A1 .Location in patent: Paragraph 0972-0973

57
[ 4334-87-6 ]
[ 6794-35-0 ]
ethyl 3-[1-methyl-6-oxo-3-(2-phenoxyphenyl)-1,6-dihydropyridazin-4-yl]benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
52%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 90℃;Inert atmosphere;	Example 59 ethyl 3-[1-methyl-6-oxo-3-(2-phenoxyphenyl)-1,6-dihydropyridazin-4-yl]benzoate [0806] Example 18B (0.090 g, 0.5 mmol), 3-(ethoxycarbonyl)phenylboronic acid (0.107 g, 0.55 mmol), Pd(PPh3)4 (0.058 g, 0.05 mmol) and sodium carbonate (0.106 g, 1.0 mmol) were combined in toluene (4 mL), ethanol (1 mL) and water (1 mL) and the mixture was degassed and left under nitrogen. The reaction mixture was heated at 90 C. for 2 hours, and then cooled to room temperature. To this solution was he added 2-phenoxyphenylboronic acid (0.150 g, 1.4 mmol). The reaction mixture was heated under reflux overnight. After cooling to room temperature, the mixture was partitioned between ethyl acetate and water. The aqueous layer was extracted with additional ethyl acetate twice. The combined organic layers were washed with brine, dried (MgSO4), filtered and concentrated. The crude product was purified by flash chromatography (silica gel, 20-50% ethyl acetate in hexanes) to provide crude material, which was further purified by reverse HPLC (C18, CH3CN/water (0.1% TFA), 0-100%) to afford 0.11 g (52%) of the title compound. 1H NMR (500 MHz, DMSO-d6) delta 7.90-7.92 (m, 1H), 7.67 (s, 1H), 7.61 (dd, J=7.63, 1.83 Hz, 1H), 7.40-7.46 (m, 2H), 7.19-7.24 (m, 3H), 7.32-7.35 (m, 1H), 7.17-7.23 (m, 3H), 7.03 (t, J=7.32 Hz, 1H), 7.00 (s, 1H), 6.56 (d, J=8.24 Hz, 1H), 6.32 (d, J=7.63 Hz, 2H), 4.21 (q, J=7.12 Hz, 2H), 3.73 (s, 3H), 1.23 (t, J=7.02 Hz, 3H). MS (DCI+) m/z 427.1 (M+H)+

Reference： [1]Patent: US2013/331382,2013,A1 .Location in patent: Paragraph 0806
[2]Patent: WO2013/185284,2013,A1

58
[ 3430-17-9 ]
[ 4334-87-6 ]
ethyl 3-(3-methylpyridin-2-yl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; In water; toluene; at 80℃; for 2h;Inert atmosphere;	Step 1: Synthesis of ethyl 3-(3-methylpyridin-2-yl)benzoate: A mixture of 2- bromo3-methylpyridine (8.00 g, 47.0 mmol) and 3-ethyloxycarbonylphenylboronic acid (10.0 g, 52.0 mmol) in toluene (200 mL) and H20 (94 mL) was added K2C03 (25.9 g, 187 mmol). The resulting mixture was degassed three times and back filled with N2. Then PdC12(dppf) (516 mg, 0.705 mmol) was added and the mixture was degassed three times and back filled with N2. The mixture was heated at 80 C for 2 hours. The mixture was diluted with EtOAc (200 mL) and filtered. The filtrate was washed with brine (50 mL), dried over anhydrous Na2504, and concentrated. The crude product was purified by silica gel column chromatography (PE/EtOAc = 3/1) to give 10.6 g (yield: 94%) of ethyl 3-(3-methylpyridin-2- yl)benzoate as a red oil.

Reference： [1]Patent: WO2014/186704,2014,A2 .Location in patent: Paragraph 00288

59
[ 373-52-4 ]
[ 4334-87-6 ]
ethyl 3-(fluoromethyl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
42%	With dmap; 1,10-Phenanthroline; (1,2-dimethoxyethane)dichloronickel(II); potassium carbonate; In 1,4-dioxane; 1,2-dimethoxyethane; at 70℃; for 24h;	To a 25 mL reaction tube was added 175 mg (0.9 mmol)3-ethoxycarbonylbenzeneboronic acid, 6.6 mg (5 mol%Mol% refers to the percentage of molar ratio of NiCl2 · DME to compound B) NiCl2 · DME (dimethylethyl ether chlorideNickel), 5.4 mg (5 mol%, mol% refers to the percentage of phen and the molar ratio of compound B) phen (1,10 &), 7.4 mg (5 mol%, mol% is the percentage of DMAP and compound B molar) DMAP (4-dimethylamineYl) pyridine), 166 mg (1.2 mmol) of K2CO3, 2 mL of ethylene glycol dimethyl ether, 1.7 mL of 1,4-dioxane,(Concentration: 2M, 0.6 mmol) of the uL CH2FBr was stirred at 70 C for 24 hours,The rate was 42%, and the purity was more than 95% by hydrogen.

Reference： [1]Angewandte Chemie - International Edition,2015,vol. 54,p. 9079 - 9083
Angew. Chem.,2015,vol. 127,p. 9207 - 9211,5
[2]Patent: CN106278847,2017,A .Location in patent: Paragraph 0070; 0071; 0072

60
[ 4334-87-6 ]
[ 10040-96-7 ]
ethyl 3-(4-imidazol-1-ylphenyl)benzoate [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2015,vol. 58,p. 9680 - 9696

61
(5-bromo-5,5-difluoropentyl)benzene [ No CAS ]
[ 4334-87-6 ]
ethyl 3-(1,1-difluoro-5-phenylpentyl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
48%	With dmap; (1,2-dimethoxyethane)dichloronickel(II); potassium carbonate; 4,4'-di-tert-butyl-2,2'-bipyridine; In Triethylene glycol dimethyl ether; at 80℃; for 24h;	To 25mL The reaction tube was added 175mg (0.9mmol) -ethoxycarbonyl-phenylboronic acid, 6.611 ^ (51] 11%, accounting refers to 5-bromo-5,5 '- difluoro the percentage of the molar amount dipentylbenzene) NiCl2 · DME, 8mg (5mo 1%) 4,4 '-dtBubpy (4,4' - di-t-butyl-bipyridine), 14.6mg (20mo 1%) DMAP, 166mg (1.2 mmo 1) K2C03,4mL triethylene glycol dimethyl ether, injection 157mg (0.6mmol) 5- bromo -5,5 '- difluoro-pentyl benzene, 80 C under stirring for 24 hours, 48% isolated yield. Purity by NMR identified more than 95,

Reference： [1]Angewandte Chemie - International Edition,2016,vol. 55,p. 5837 - 5841
Angew. Chem.,2016,vol. 128,p. 5931 - 5935,5
[2]Patent: CN105669365,2016,A .Location in patent: Paragraph 0146-0148

62
[ 88-12-0 ]
[ 383-62-0 ]
[ 4334-87-6 ]
ethyl 3-(4-ethoxy-3,3-difluoro-4-oxo-1-(2-oxopyrrolidin-1-yl)butyl)benzoate [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2016,vol. 55,p. 12270 - 12274
Angew. Chem.,2016,vol. 128,p. 12458 - 12462,5

63
[ 4334-87-6 ]
[ 128372-89-4 ]
(S)-4-(3-ethoxycarbonylphenyl)-2-oxopiperidine-1-carboxylic acid tert-butyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With chloro(1,5-cyclooctadiene)rhodium(I) dimer; potassium carbonate; (S)-(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine); In 1,4-dioxane; water; at 45℃;Inert atmosphere;	3-Carbethoxyphenylboronic acid (6.0 g, 31 mmol, 2.2 equiv) was dissolved in dioxane (50 mL) and cooled in an ice bath. K2CO3 (4.6 g, 33 mmol, 2.4 equiv) was added followed by H2O (5 mL). N2 was bubbled through the solution for 2 min, then (Rh(cod)Cl)2 (600 mg, 1.2 mmol, 0.08 equiv) and (S)-BINAP (1.68 g, 2.56 mmol, 0.18 equiv) was added. N2 was bubbled through the solution for 5 more min, then 6-oxo-3,6-dihydro-2H-pyridine-1- carboxylic acid tert-butyl ester (2.70 g, 14 mmol, 1 equiv) was added slowly. N2 was bubbled through the solution for 5 more min, then the reaction was allowed to warm to room temperature over 1 h. The reaction was heated to 45 C for 1 h, then was allowed to cool to room temperature and stirred overnight. The reaction was diluted with EtOAc, washed with H2O, then brine and then concentrated. The residue was purified by silica gel chromatography (5% to 20% EtOAc in hexanes) to give (S)-4-(3-ethoxycarbonyl-phenyl)-2- oxo-piperidine-1-carboxylic acid tert-butyl ester (3.5 g, 74%).

Reference： [1]Patent: WO2016/187393,2016,A1 .Location in patent: Paragraph 0196

64
[ 380626-56-2 ]
[ 4334-87-6 ]
1,3,5-tris(3'(ethoxycarbonyl)biphenyl-2-yl)benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 70℃; for 48.25h;Inert atmosphere;	1,3,5-Tris-2'-bromophenylbenzene 15 (500 mg, 0.921 mmol),3-(ethoxycarbonyl)phenylboronic acid 18 (894 mg, 4.61 mmol),K2CO3 (1.15 g, 8.30 mmol) and Pd(PPh3)4 (29 mg, 0.0249 mmol)were added to a mixture of toluene (90 cm3), ethanol (10 cm3)and water (10 cm3) which was then heated at 70 C and purgedwith N2 for 15 min. The reaction mixture was stirred at 70 C for2 days before being allowed to cool. The reaction mixture was filtered,and water (50 cm3) was added to the filtrate which wasextracted into toluene. The toluene extract was then washed withwater (4 30 cm3) and brine (2 30 cm3), dried over MgSO4 andconcentrated under reduced pressure to give an orange oil whichwas purified by column chromatography (15% ethyl acetate in hexaneon silica) to give Et3L4 as a white solid (yield 387 mg, 56%). 1HNMR (CDCl3, 400 MHz) delta 8.04 (t, J = 1.5 Hz, 3H), 7.89 (dt, J = 7.7,1.3 Hz, 3H), 7.27-7.43 (m, 12H), 7.00 (dt, J = 7.8, 1.3 Hz, 3H), 6.8(d, J = 7.4 Hz, 3H), 7.76 (s, 3H), 4.39 (q, J = 7.1, 6H), 1.39 (t, J = 7.1,9H). ESI-TOF-HRMS: m/z Calc. for C51H42 O6Na: 773.2879. Found773.2771 [M+Na]+. Elemental Anal. Calc. for C51H42O6: C, 81.58;H, 5.64. Found: C, 81.50; H, 5.22%.

Reference： [1]Polyhedron,2016,vol. 120,p. 18 - 29

65
[ 75-45-6 ]
[ 4334-87-6 ]
[ 1217088-28-2 ]

Yield	Reaction Conditions	Operation in experiment
78%	With tris-(dibenzylideneacetone)dipalladium(0); potassium carbonate; hydroquinone; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In 1,4-dioxane; at 110℃; for 48h;Inert atmosphere; Sealed tube;	General procedure: To a 25 ml sealed tube were added anhydrous K2CO3 (powder, 4.0 equiv.), hydroquinone (2.0 equiv.), Pd2(dba)3 (2.5 mol%), Xantphos (7.5 mol%) and ArB(OH)2 (0.3 or 0.5 mmol) or Ar-Beg (0.3 or 0.5 mmol) under argon. A solution of ClCF2H in 1,4-dioxane (2.0 M, 1.5 ml for 0.3 mmol scale or 2.5 ml for 0.5 mmol scale, 10 equiv.) and fresh distilled 1,4-dioxane (1.0 ml for 0.3 mmol scale or 2.5 ml for 0.5 mmol scale) were added subsequently. The sealed tube was screw capped and heated to 110 C (oil bath). After stirring for 48 h, the reaction was cooled to room temperature and fluorobenzene (1.0 equiv.) was added. The yield was determined by 19F NMR before working up. The reaction mixture was then diluted with ethyl acetate, filtered through a pad of Celite and concentrated. The residue was purified with silica gel chromatography to provide the desired product.

Reference： [1]Nature Chemistry,2017,vol. 9,p. 918 - 923

66
1-(3,5-bis(trifluoromethyl)phenyl)-3-(4-bromo-2,2-dimethylpent-4-en-1-yl)urea [ No CAS ]
[ 4334-87-6 ]
ethyl 3-(5-(3-(3,5-bis(trifluoromethyl)phenyl)ureido)-4,4-dimethylpent-1-en-2-yl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
20%	With palladium diacetate; potassium carbonate; XPhos; In water; acetonitrile; at 80℃; for 12h;Inert atmosphere;	To 1 aa (2.0 mmol), 3 - ethoxy carbonyl phenyl boronic acid (3.0 mmol), K2CO3(6.0 mmol) and 2 - dicyclohexyl phosphino -2 ', 4', 6' - three isopropyl biphenyl (X - Phos, 0.16 mmol) of CH3CN/H2O (6.0 ml/3.0 ml) added in the solution Pd (OAc)2(0.08 mmol). Then the flask transient vacuum pumping and backfilling with argon three times. After the completion of the, sealing the flask, the reaction mixture in the argon, 80 C stirring for 12 hours. Then, the reaction mixture is cooled to room temperature, EtOAc for extraction. The combined organic layer using salt water washing, Na for2SO4Drying and vacuum concentrated, to get the crude product, and further purification by silica gel column chromatography (eluant: petroleum ether/EtOAc=100/1 to 7/1), to obtain 1 y (0.4 mmol, 20% yield).

Reference： [1]Patent: CN107253928,2017,A .Location in patent: Paragraph 0105; 0108
[2]Chem,2017,vol. 3,p. 979 - 990

67
[ 19362-89-1 ]
[ 4334-87-6 ]
[ 134752-72-0 ]

Yield	Reaction Conditions	Operation in experiment
65%	With potassium phosphate; palladium diacetate; XPhos; In tetrahydrofuran; at 50℃; for 14h;Sealed tube; Inert atmosphere;	General procedure: The desired amount of substrate, boronic acid (3 equiv), base (3equiv), Pd(OAc)2 (2.5 mol%) and ligand (5 mol%) were weighed out as solids, the vial was sealed and purged with argon, then solvent was added and the vial was purged again. The reactions were run for 14 h at the specified temperature. The crude material was filtered through a pad of Celite and washed three times with CHCl3. The solvent was removed under reduced pressure, an internal standard was added and the reaction was analysed by 1H NMR spectroscopy. For purification, the analysed mixture was concentrated, the product extracted with Et2O and filtered through anhydrous MgSO4 and further purified by flash column chromatography.

Reference： [1]Synthesis,2018,vol. 50,p. 793 - 803

68
[ 4334-87-6 ]
[ 174680-55-8 ]
2-amino-5-(3-ethoxycarbonylphenyl)-3-benzylpyrazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With bis(benzonitrile)palladium(II) dichloride; [1,4-bis(diphenylphosphino)butane] palladium(ll) dichloride; potassium carbonate; In water; toluene; at 109℃; for 6h;Inert atmosphere;	The intermediate 2-amino-5-bromo-3-benzyl-pyrazine (100 mg, 0.378 mmol),(II) (10 mg, 0.026 mmol), [1,4-bis (diphenylphosphino) butane] palladium (II) dichloride (20 mg, 0.033 mmol) was dissolved in 6 mL of toluene in,Then 3-methoxy was addedCarbonyl carbonyl boronic acid(110 mg, 0.576 mmol) and aqueous potassium carbonate (2 M, 0.3 mL). The mixture was stirred at 109 C for 6 hours under reflux. After the reaction was stopped, the reaction mixture was filtered and the filtrate was concentrated. Ethyl acetate and saturated sodium chloride solution were added thereto. After the extraction, the ethyl acetate layer was dried over anhydrous sodium sulfate and filtered to obtain 90 mg of a yellow solid on a 200-300 mesh silica gel column. Yield 74%.

Reference： [1]Patent: CN105968114,2016,A .Location in patent: Paragraph 0144; 0145; 0180-0182

69
[ 3017-70-7 ]
[ 4334-87-6 ]
(E)-ethyl 3-[1-chloro-3-methyl-4-(4-methylphenylsulfonamido)but-2-en-2-yl]benzoate [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2018,vol. 2018,p. 1248 - 1254

70
[ 3017-70-7 ]
[ 4334-87-6 ]
[ 35925-86-1 ]

Reference： [1]European Journal of Organic Chemistry,2018,vol. 2018,p. 1248 - 1254

71
[ 3132-99-8 ]
[ 4334-87-6 ]
ethyl 3'-formyl-[1,1'-biphenyl]-3-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%		Tetrakis triphenylphosphine palladium (59 mg,0.05 mmol) and intermediate 12.1 (0.19 mL,1.70 mmol) were dissolved in DME (5 mL). To another flask was added K2CO3,compound 12.2 (300 mg,1.54 mmol), and DME (5 mL) and the resulting mixture was stirred 10 min. The solutions were mixed together via cannula. Stirring was continued at 110 C for 20 h. The crude reaction mixture was poured in water,acidified with 3N HC1 and extracted with EtOAc (3 x 20 mL). The organic phase was washed with brine and dried over Na2S04. Flash chromatography purification (eluent PET/EtOAc,0-20%) of the reaction mixture afforded the title compound 12.3 (280 mg,1.1 mmol) as colored oil. Yield 65%;XH NMR (400 MHz,CDCI3) delta 1.44 (t,J = 7.1 Hz,3H), 4.44 (q, / = 7.1 Hz,2H), 7.56 (t, / = 7.7 Hz,1H), 7.65 (t, / = 7.6 Hz,1H), 7.82 (d, / = 7.7 Hz,1H), 7.91 (d,7.6 Hz,2H), 8.09 (d, / = 7.8 Hz,1H), 8.14 (s,1H), 8.07 (s,1H), 10.11 (s,1H).

Reference： [1]Patent: WO2018/69532,2018,A1 .Location in patent: Paragraph 0547; 0563

72
[ 4334-87-6 ]
[ 57381-37-0 ]
ethyl 4'-chloro-2'-cyano-[1,1'-biphenyl]-3-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84.2%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate; at 80℃; for 2h;Sealed tube; Inert atmosphere;	A microwave reaction vessel was charged with (3-(ethoxycarbonyl)phenyl)boronic acid (427 mg, 2.2 mmol), <strong>[57381-37-0]2-bromo-5-chlorobenzonitrile</strong> (433 mg, 2 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (82 mg, 0.2 mmol), potassium phosphate tribasic (1.27 g, 6 mmol), and palladium(II) acetate (22.5 mg, 0.1 mmol) and was sealed. It was put under vacuum and filled with argon (3x repeated). Then the degassed toluene was added and the suspension was stirred at 80C for 2 hours. The reaction mixture was then allowed to cool to room temperature, diluted with 5 ml EtOAc and filtered through a thin bed of silica (0.3-0.5 mm) and eluted/washed with EtOAc (ca. 40 ml) and concentrated under reduced pressure. After Si02 flash chromatography, ethyl 4'-chloro-2'-cyano-[1,1'-biphenyl]-3-carboxylate was obtained as a off-white, crystalline solid (481 mg, 84.2%). MS (ESI): m/z = 286.1 [M+H]+.

Reference： [1]Patent: WO2018/189063,2018,A1 .Location in patent: Page/Page column 34; 35

73
[ 4334-87-6 ]
2-bromo-6-chlorobenzonitrile [ No CAS ]
ethyl 3-(3-chloro-2-cyanophenyl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
44.4%		To a solution of <strong>[4334-87-6](3-(ethoxycarbonyl)phenyl)boronic acid</strong> (350 mg, 1.8 mmol, Eq: 1.3) in THF (5 mL) was added 2-bromo-6-chlorobenzonitrile (300 mg, 1.39 mmol, Eq: 1) and potassium fluoride (242 mg, 4.16 mmol, Eq: 3). The reaction mixture was degassed under a slight argon flush in an ultrasonic bath for 15 minutes. palladium(II) acetate (6.22 mg, 27.7 muiotaetaomicron, Eq: 0.02) and (2-biphenyl)di-tert-butylphosphine (16.5 mg, 55.4 mumol, Eq: 0.04) was added. The reaction mixture was stirred for 18 hours at 50C. The reaction mixture was poured on 30 mL water and 30 mL EtOAc and the layers were separated. The aqueous layer was extracted a second time with 30 mL EtOAc. The organic layers were washed with 30 mL brine, dried over MgSO4, filtered and concentrated under vacuum. The residue was purified by silica gel chromatography to yield ethyl 3-(3-chloro-2-cyanophenyl)benzoate as a white foam (188 mg, 44.4%). GC-MS: m/z = 285.1

Reference： [1]Patent: WO2018/189063,2018,A1 .Location in patent: Page/Page column 36

74
[ 42872-83-3 ]
[ 4334-87-6 ]
ethyl 3-(2-cyano-4-methylphenyl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94.3%		To a solution of (3-(ethoxycarbonyl)phenyl)boronic acid (386 mg, 1.99 mmol, Eq: 1.3) in THF (5 mL) was added <strong>[42872-83-3]2-bromo-5-methylbenzonitrile</strong> (300 mg, 1.53 mmol, Eq: 1) and potassium fluoride (267 mg, 4.59 mmol, Eq: 3). The reaction mixture was degassed under a slight argon flush in an ultrasonic bath for 15 minutes. palladium(II) acetate (6.87 mg, 30.6 muiotaetaomicron, Eq: 0.02) and (2-biphenyl)di-tert-butylphosphine (18.3 mg, 61.2 muiotaetaomicron, Eq: 0.04) was added. The reaction mixture was stirred for 18 hours at 50C. The reaction mixture was poured on 30 mL water and 30 mL EtOAc and the layers were separated. The aqueous layer was extracted a second time with 30 mL EtOAc. The organic layers were washed with 30 mL brine, dried over MgSO4, filtered and concentrated under vacuum. The residue was purified by silica gel chromatography to yield ethyl 3-(2-cyano-4-methylphenyl)benzoate as a white solid (383 mg, 94.3%). MS (ESI): m/z = 266.118 [M+H]+.

Reference： [1]Patent: WO2018/189063,2018,A1 .Location in patent: Page/Page column 38

75
[ 4334-87-6 ]
C₁₄H₁₈BrN₂O₃P [ No CAS ]
C₂₃H₂₇N₂O₅P [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 100℃;Inert atmosphere;	To a three-neck roundbottomflask under argon atmosphere was added Pd(PPh3)4 (0.1eq.), DMF (27 mL) and compounds 15 (3.65 mmol). K2CO3 (3 eq.)and the corresponding 3-ethoxycarbonylbenzeneboronic acid (1.7eq.) were successively added and the reaction mixture was stirredunder argon at 100 C until TLC revealed that the starting materialwas consumed. The mixture was cooled to room temperature,diluted with water and product was extracted with EtOAc. Theorganic layers were combined, dried over MgSO4, concentrated invacuum and the residue was purified by silica gel column chromatography(CH2Cl2/MeOH, 0-5%) to provide the desired compound16.Yield 86%; 1H NMR (CDCl3): delta 1.31 (t, J 7.2 Hz, 6H), 1.42 (t,J 7.2 Hz, 3H), 4.13 (q, J 6.9 Hz, 4H), 4.34 (d, 2H, 3J 12.3 Hz), 4.40(q, J 6.9 Hz, 2H), 7.34-8.32 (m, 10H); 31P NMR: 17.5. MS (ESI) m/z885 [2 MH]; 443 [MH]

Reference： [1]European Journal of Medicinal Chemistry,2019,vol. 168,p. 28 - 44

76
[ 623-00-7 ]
[ 4334-87-6 ]
[ 131379-34-5 ]

Yield	Reaction Conditions	Operation in experiment
71%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 100℃;Inert atmosphere;	General procedure: To a three-neck round-bottom flask under argon atmospherewas added Pd(PPh3)4 (0.14 mmol), DMF (9.5 mL) and commerciallyavailable 2-, 3- or 4-bromobenzonitrile (1.41 mmol). K2CO3(4.24 mmol) and the corresponding 2-, 3- or 4-ethoxycarbonylbenzeneboronic acid (2.40 mmol) were successivelyadded and the reaction mixture was stirred under argon at100 C until TLC revealed that the starting material was consumed.The mixture was cooled to room temperature, diluted with waterand product was extracted with EtOAc. Organic layers were driedover MgSO4, concentrated in vacuum and the residue was purifiedby silica gel column chromatography (petroleum ether/EtOAc,0-60%) to provide the desired compounds.

Reference： [1]European Journal of Medicinal Chemistry,2019,vol. 168,p. 28 - 44

77
[ 6952-59-6 ]
[ 4334-87-6 ]
[ 1072438-69-7 ]

Yield	Reaction Conditions	Operation in experiment
74%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 100℃;Inert atmosphere;	General procedure: To a three-neck round-bottom flask under argon atmospherewas added Pd(PPh3)4 (0.14 mmol), DMF (9.5 mL) and commerciallyavailable 2-, 3- or 4-bromobenzonitrile (1.41 mmol). K2CO3(4.24 mmol) and the corresponding 2-, 3- or 4-ethoxycarbonylbenzeneboronic acid (2.40 mmol) were successivelyadded and the reaction mixture was stirred under argon at100 C until TLC revealed that the starting material was consumed.The mixture was cooled to room temperature, diluted with waterand product was extracted with EtOAc. Organic layers were driedover MgSO4, concentrated in vacuum and the residue was purifiedby silica gel column chromatography (petroleum ether/EtOAc,0-60%) to provide the desired compounds.

Reference： [1]European Journal of Medicinal Chemistry,2019,vol. 168,p. 28 - 44

78
[ 2042-37-7 ]
[ 4334-87-6 ]
[ 131379-35-6 ]

Yield	Reaction Conditions	Operation in experiment
92%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 100℃;Inert atmosphere;	General procedure: To a three-neck round-bottom flask under argon atmospherewas added Pd(PPh3)4 (0.14 mmol), DMF (9.5 mL) and commerciallyavailable 2-, 3- or 4-bromobenzonitrile (1.41 mmol). K2CO3(4.24 mmol) and the corresponding 2-, 3- or 4-ethoxycarbonylbenzeneboronic acid (2.40 mmol) were successivelyadded and the reaction mixture was stirred under argon at100 C until TLC revealed that the starting material was consumed.The mixture was cooled to room temperature, diluted with waterand product was extracted with EtOAc. Organic layers were driedover MgSO4, concentrated in vacuum and the residue was purifiedby silica gel column chromatography (petroleum ether/EtOAc,0-60%) to provide the desired compounds.

Reference： [1]European Journal of Medicinal Chemistry,2019,vol. 168,p. 28 - 44

79
[ 4334-87-6 ]
N-[5-(7-bromo-4-oxoquinazolin-3(4H)-yl)-2-(trifluoromethoxy)phenyl]-1-(morpholin-4-yl)cyclopropanecarboxamide [ No CAS ]
ethyl 3-{3-[3-([1-(morpholin-4-yl)cyclopropyl]carbonyl}amino)-4-(trifluoromethoxy)phenyl]-4-oxo-3,4-dihydroquinazolin-7-yl}benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate; In 1,2-dimethoxyethane; water; N,N-dimethyl-formamide; at 80℃; for 1h;Inert atmosphere;	A mixture of N-[5-(7-bromo-4-oxoquinazolin-3(4H)-yl)-2-(trifluoromethoxy)phenyl]-l -(morpholin-4- yl)cyclopropanecarboxamide (40.0 mg, 98% purity, 70.8 muetaiotaomicron), <strong>[4334-87-6][3-(ethoxycarbonyl)-phenyl]boronic acid</strong> (19.1 mg, 97% purity, 95.6 muetaiotaomicron), [l,l-Bis-(Diphenylphosphino)-ferrocen]-Dichloropalladium- Dichloromethane -complex (2.89 mg, 3.54 muetaiotaomicron) and potassium carbonate (19.6 mg, 142 muetaiotaomicron) in N,N- dimethylformamide (62 mu), water (250 mu) and 1,2-dimethoxyethane (340 mu) was degassed by passing argon through it for 5 min and then the mixture was heated at 80C for 1 h. The reaction mixture was filtered through a silica column eluting with a gradient of dichloromethane/methanol from 100:0 to 90: 10. The material obtained was then submitted to preparative HPLC 125x30mm with acetonitrile/water (0.2% ammonia) to deliver 40.7 mg (92 % yield) of the title compound.LC-MS (Method 6): Rt= 2.43 min; MS (ESIpos): m/z = 623 [M+H]+-NMR (400 MHz, DMSO-d6) delta [ppm] : 0.008 (1.25), 1.119 (1.53), 1.131 (4.26), 1.139 (4.81), 1.149 (2.24), 1.273 (2.05), 1.283 (4.70), 1.291 (3.89), 1.303 (1.59), 1.351 (7.48), 1.368 (16.00), 1.386 (7.62), 2.328 (0.48), 2.472 (6.57), 2.670 (0.64), 3.708 (6.44), 4.356 (2.19), 4.374 (7.11), 4.392 (7.03), 4.410 (2.13), 7.432 (2.36), 7.438 (2.37), 7.453 (2.73), 7.460 (2.78), 7.695 (2.15), 7.707 (2.45), 7.714 (4.40), 7.734 (2.86), 7.957 (2.19), 7.961 (2.30), 7.978 (2.29), 7.982 (2.64), 8.048 (6.45), 8.052 (7.03), 8.071 (2.43), 8.143 (2.10), 8.163 (2.10), 8.293 (4.39), 8.314 (3.82), 8.333 (4.46), 8.430 (9.94), 8.578 (5.07), 8.584 (5.08), 10.628 (4.47).

Reference： [1]Patent: WO2019/63704,2019,A1 .Location in patent: Page/Page column 181; 182

80
[ 4334-87-6 ]
[ 439612-51-8 ]
ethyl 3-(3-isopropyl-1H-indol-5-yl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With potassium phosphate; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In tetrahydrofuran; water; at 75℃; for 16h;Inert atmosphere;	A mixture of 5-bromo-3-isopropyl-lH-indole (1.00 g, 4.20 mmol), (3- (ethoxycarbonyl)phenyl)boronic acid (0.978 g, 5.04 mmol) and tripotassium phosphate (2.67 g, 12.60 mmol) in THF (20 mL) and water (4 mL) was degassed for 10 min with nitrogen gas. Next, PdChidppO-CEhCh adduct (0.086 g, 0.105 mmol) was added and the mixture was stirred at 75 C for 16 h. The reaction mixture was diluted with EtOAc (50 mL), washed with water (30 mL), brine (10 mL), dried (Na2SCri) and concentrated to get crude material. The crude material was purified by silica gel chromatography (ISCO) using 24 g silica column, compound was eluted in 10% EtOAc in hexanes, the fractions were collected and concentrated to afford ethyl 3-(3-isopropyl-lH-indol-5-yl)benzoate (1.021 g, 3.32 mmol, 79 % yield) as a pale yellow solid. LCMS retention time 1.21 min [B] MS m/r. 308 (M+H).

Reference： [1]Patent: WO2019/126253,2019,A1 .Location in patent: Page/Page column 67-68

81
[ 4334-87-6 ]
3-(difluoromethyl)-4-iodo-1-methyl-1H-pyrazole [ No CAS ]
C₁₄H₁₄F₂N₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate; In 1,4-dioxane; water; at 110℃;Inert atmosphere;	Under N2 protection conditions, 1.94 mmol IV-1,2.33 mmol of 3-ethoxycarbonylbenzeneboronic acid,3.88 mmol of cesium carbonate and 0.1 mmol1,1'-bisdiphenylphosphinoferrocene palladium dichloride [Pd(dppf)Cl2] dissolved in 15 ml1,4-dioxane/water (10:1, volume/volume) in a mixed solvent;Heat under reflux at 110 C overnight. After the reaction is completed, it is cooled to room temperature.The mixture was filtered under reduced pressure with a pad of Celite, and washed with ethyl acetate.Purified by column chromatography with petroleum ether / ethyl acetate (8:1, v/v) eluent.Obtaining the target product V-1, the yield is 65%;

Reference： [1]Patent: CN109970650,2019,A .Location in patent: Paragraph 0046-0048

82
[ 201230-82-2 ]
(4,4,4-trifluoro-3-iodobutyl)benzene [ No CAS ]
[ 4334-87-6 ]
C₂₀H₁₉F₃O₃ [ No CAS ]

Reference： [1]ACS Catalysis,2020,vol. 10,p. 36 - 42

83
[ 201230-82-2 ]
[ 4334-87-6 ]
C₉H₁₀F₃IO [ No CAS ]
C₁₉H₁₉F₃O₄ [ No CAS ]

Reference： [1]ACS Catalysis,2020,vol. 10,p. 36 - 42

84
[ 10075-50-0 ]
[ 4334-87-6 ]
ethyl 3-(1H-indol-5-yl)-benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate In toluene at 100℃; for 17.5h; Schlenk technique; Inert atmosphere;	General procedure (GP5): Suzuki coupling (SPhos) General procedure: A Schlenk tube was dried under vacuum, filled with nitrogen and charged consecutively with 1.00 eq bromoarene, 1.50 eq boronic acid, 2.00 eq mortar powdered, anhydrous K3PO4, 0.01 eq Pd(OAc)2, 0.02 eq SPhos, and abs. toluene (2 mL/0.5 mmol bromoarene). The mixture was degassed by vacuum/N2 cycles and stirred at 100 °C. As TLC analysis or GC-MS analysis showed full conversion of the starting material, the mixture was cooled to rt and filtered through a pad of celite, which was rinsed

Reference： [1]Breinbauer, Rolf; Doler, Carina; Fuchs, Elisabeth; Grabner, Gernot F.; Mayer, Nicole; Melcher, Michaela-Christina; Migglautsch, Anna K.; Romauch, Matthias; Schweiger, Martina; Zechner, Rudolf; Zimmermann, Robert [Bioorganic and medicinal chemistry, 2020, vol. 28, # 16]

85
[ 4334-87-6 ]
[ 99-90-1 ]
ethyl 4`-acetylbiphenyl-3-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate In toluene at 100℃; for 3.5h; Schlenk technique; Inert atmosphere;	General procedure (GP5): Suzuki coupling (SPhos) General procedure: A Schlenk tube was dried under vacuum, filled with nitrogen and charged consecutively with 1.00 eq bromoarene, 1.50 eq boronic acid, 2.00 eq mortar powdered, anhydrous K3PO4, 0.01 eq Pd(OAc)2, 0.02 eq SPhos, and abs. toluene (2 mL/0.5 mmol bromoarene). The mixture was degassed by vacuum/N2 cycles and stirred at 100 °C. As TLC analysis or GC-MS analysis showed full conversion of the starting material, the mixture was cooled to rt and filtered through a pad of celite, which was rinsed

Reference： [1]Breinbauer, Rolf; Doler, Carina; Fuchs, Elisabeth; Grabner, Gernot F.; Mayer, Nicole; Melcher, Michaela-Christina; Migglautsch, Anna K.; Romauch, Matthias; Schweiger, Martina; Zechner, Rudolf; Zimmermann, Robert [Bioorganic and medicinal chemistry, 2020, vol. 28, # 16]

86
[ 60724-47-2 ]
[ 4334-87-6 ]
ethyl 3-(5-((dimethylamino)methyl)furan-2-yl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate In toluene at 100℃; Schlenk technique; Inert atmosphere;	General procedure (GP5): Suzuki coupling (SPhos) General procedure: A Schlenk tube was dried under vacuum, filled with nitrogen and charged consecutively with 1.00 eq bromoarene, 1.50 eq boronic acid, 2.00 eq mortar powdered, anhydrous K3PO4, 0.01 eq Pd(OAc)2, 0.02 eq SPhos, and abs. toluene (2 mL/0.5 mmol bromoarene). The mixture was degassed by vacuum/N2 cycles and stirred at 100 °C. As TLC analysis or GC-MS analysis showed full conversion of the starting material, the mixture was cooled to rt and filtered through a pad of celite, which was rinsed

Reference： [1]Breinbauer, Rolf; Doler, Carina; Fuchs, Elisabeth; Grabner, Gernot F.; Mayer, Nicole; Melcher, Michaela-Christina; Migglautsch, Anna K.; Romauch, Matthias; Schweiger, Martina; Zechner, Rudolf; Zimmermann, Robert [Bioorganic and medicinal chemistry, 2020, vol. 28, # 16]

87
[ 4334-87-6 ]
1-((5-bromofuran-2-yl)methyl)-4-(methylsulfonyl)piperazine [ No CAS ]
ethyl 3-(5-((4-(methylsulfonyl)piperazin-1-yl)methyl)furan-2-yl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate In toluene at 100℃; Schlenk technique; Inert atmosphere;	General procedure (GP5): Suzuki coupling (SPhos) General procedure: A Schlenk tube was dried under vacuum, filled with nitrogen and charged consecutively with 1.00 eq bromoarene, 1.50 eq boronic acid, 2.00 eq mortar powdered, anhydrous K3PO4, 0.01 eq Pd(OAc)2, 0.02 eq SPhos, and abs. toluene (2 mL/0.5 mmol bromoarene). The mixture was degassed by vacuum/N2 cycles and stirred at 100 °C. As TLC analysis or GC-MS analysis showed full conversion of the starting material, the mixture was cooled to rt and filtered through a pad of celite, which was rinsed

Reference： [1]Breinbauer, Rolf; Doler, Carina; Fuchs, Elisabeth; Grabner, Gernot F.; Mayer, Nicole; Melcher, Michaela-Christina; Migglautsch, Anna K.; Romauch, Matthias; Schweiger, Martina; Zechner, Rudolf; Zimmermann, Robert [Bioorganic and medicinal chemistry, 2020, vol. 28, # 16]

88
[ 4334-87-6 ]
3-(N-hydroxycarbamoyl)benzeneboronic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89.5%	With potassium etoxide; hydroxylammonium sulfate In ethanol at 0 - 35℃; for 3h;	5 Example 5 In a four-neck jacketed glass bottle,Put into hydroxylamine sulfate (44.3g, 0.27mol) and 170mL absolute ethanol, cool down to 0-5°C and add dropwise 20% sodium ethoxide/ethanol solution (199g, 0.54mol),3-methoxycarbonylbenzeneboronic acid (87.3 g, 0.45 mol) was added in portions,Subsequently, a 20% sodium ethoxide ethanol solution (199 g, 0.54 mol) was added dropwise, and the temperature was raised to 30-35 ° C for 3 hours.Cool to 0-5, add 1M hydrochloric acid dropwise to adjust pH=1.0-1.5, filter,The filter cake is rinsed with water, the filter cake is slurried with acetone, and driedget3-N-Hydroxycarbamoylbenzeneboronic acid72.9g, HPLC 99.5%,Yield 89.5%.

Reference： [1]Current Patent Assignee: CHINA SYNCHEM TECH CO LTD - CN114262340, 2022, A Location in patent: Paragraph 0046-0048

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
{[ item.p_purity ]}	{[ item.pr_size ]}	{[ getRatePrice(item.pr_usd, 1,1) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]}	{[ getRatePrice(item.pr_usd, 1,1) ]}	Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} {[ getRatePrice(item.pr_usd,1,item.mem_rate) ]}	{[ item.pr_usastock ]}	Inquiry -	{[ item.pr_chinastock ]}	Inquiry -

CAS No. :	4334-87-6	MDL No. :	MFCD02179444
Formula :	C₉H₁₁BO₄	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	REHVCPNQQBDOJJ-UHFFFAOYSA-N
M.W :	193.99	Pubchem ID :	3249312
Synonyms :

Num. heavy atoms :	14
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.22
Num. rotatable bonds :	4
Num. H-bond acceptors :	4.0
Num. H-bond donors :	2.0
Molar Refractivity :	52.35
TPSA :	66.76 Å²

GI absorption :	High
BBB permeant :	No
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.74 cm/s

Log Po/w (iLOGP) :	0.0
Log Po/w (XLOGP3) :	1.05
Log Po/w (WLOGP) :	-0.46
Log Po/w (MLOGP) :	0.52
Log Po/w (SILICOS-IT) :	-0.52
Consensus Log Po/w :	0.12

[ CAS No. 4334-87-6 ] {[proInfo.proName]}

Quality Control of [ 4334-87-6 ]

Related Doc. of [ 4334-87-6 ]

Product Details of [ 4334-87-6 ]

Calculated chemistry of [ 4334-87-6 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 4334-87-6 ]

Application In Synthesis of [ 4334-87-6 ]

[ 4334-87-6 ] Synthesis Path-Upstream 1~1

[ 4334-87-6 ] Synthesis Path-Downstream 1~88

Related Functional Groups of
[ 4334-87-6 ]

Organoboron

Aryls

Esters

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.55

Log S (ESOL) :	-1.76
Solubility :	3.39 mg/ml ; 0.0175 mol/l
Class :	Very soluble
Log S (Ali) :	-2.04
Solubility :	1.76 mg/ml ; 0.00906 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-1.77
Solubility :	3.27 mg/ml ; 0.0169 mol/l
Class :	Soluble

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	2.02

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	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.
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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

[ CAS No. 4334-87-6 ] {[proInfo.proName]}

Quality Control of [ 4334-87-6 ]

Related Doc. of [ 4334-87-6 ]

Product Details of [ 4334-87-6 ]

Calculated chemistry of [ 4334-87-6 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 4334-87-6 ]

Application In Synthesis of [ 4334-87-6 ]

[ 4334-87-6 ] Synthesis Path-Upstream 1~1

[ 4334-87-6 ] Synthesis Path-Downstream 1~88

Related Functional Groups of [ 4334-87-6 ]

Organoboron

Aryls

Esters

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

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[ 4334-87-6 ]