[ CAS No. 55499-43-9 ] {[proInfo.proName]}

Name: 55499-43-9|3,4-Dimethylphenylboronic acid|97%
Brand: Ambeed
SKU: A204724
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Quality Control of [ 55499-43-9 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 55499-43-9 ]

SDS Specification

Alternatived Products of [ 55499-43-9 ]

Product Details of [ 55499-43-9 ]

CAS No. :	55499-43-9	MDL No. :	MFCD01009694
Formula :	C₈H₁₁BO₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	KDVZJKOYSOFXRV-UHFFFAOYSA-N
M.W :	149.98	Pubchem ID :	2734348
Synonyms :

Calculated chemistry of [ 55499-43-9 ]

Physicochemical Properties

Num. heavy atoms :	11
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.25
Num. rotatable bonds :	1
Num. H-bond acceptors :	2.0
Num. H-bond donors :	2.0
Molar Refractivity :	46.2
TPSA :	40.46 Å²

Pharmacokinetics

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) :	-6.11 cm/s

Lipophilicity

Log Po/w (iLOGP) :	0.0
Log Po/w (XLOGP3) :	1.56
Log Po/w (WLOGP) :	-0.02
Log Po/w (MLOGP) :	0.94
Log Po/w (SILICOS-IT) :	0.15
Consensus Log Po/w :	0.53

Druglikeness

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

Water Solubility

Log S (ESOL) :	-2.09
Solubility :	1.22 mg/ml ; 0.00812 mol/l
Class :	Soluble
Log S (Ali) :	-2.02
Solubility :	1.43 mg/ml ; 0.00956 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-2.04
Solubility :	1.36 mg/ml ; 0.00904 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.52

Safety of [ 55499-43-9 ]

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:

Application In Synthesis of [ 55499-43-9 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 55499-43-9 ]
Downstream synthetic route of [ 55499-43-9 ]

[ 55499-43-9 ] Synthesis Path-Upstream 1~9

1
[ 201230-82-2 ]
[ 640-60-8 ]
[ 55499-43-9 ]
[ 2571-39-3 ]

Reference： [1] RSC Advances, 2016, vol. 6, # 89, p. 86502 - 86509

2
[ 201230-82-2 ]
[ 17763-67-6 ]
[ 55499-43-9 ]
[ 2571-39-3 ]

Reference： [1] RSC Advances, 2016, vol. 6, # 89, p. 86502 - 86509

3
[ 55499-43-9 ]
[ 611-73-4 ]
[ 2571-39-3 ]

Reference： [1] RSC Advances, 2014, vol. 4, # 89, p. 48698 - 48702

4
[ 255837-23-1 ]
[ 55499-43-9 ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: With tris(dibenzylideneacetone)dipalladium⁽⁰⁾ chloroform complex; diisopropopylaminoborane; triethylamine; triphenylphosphine In tetrahydrofuran at 65℃; for 12 h; Inert atmosphere Stage #2: With methanol In tetrahydrofuran at 0℃; Inert atmosphere	General procedure: Triphenylphosphene (0.131 g, 0.5 mmol, 20 mol percent), p-iodoanisol (0.585 g, 2.5 mmol), and triethylamine (1.78 mL, 12.5 mmol) were added to a 50 mL round-bottomed flask equipped with a sidearm, condenser, and stir bar. This solution was then degassed by alternating vacuum and argon three times. Palladium dichloride (0.023 g, 0.13 mmol, 5 mol percent) was then added under positive argon pressure. After stirring at room temperature for 15 min, diisopropylaminoborane (5 mL, 1 M solution in THF, 5 mmol) was added and the reaction mixture was degassed again by alternating vacuum and argon three times. The reaction solution was then heated to reflux. After 12 h of reflux the reaction was cooled to 0 °C and 6 mL of methanol was added through the condenser slowly (Caution: exothermic reaction with evolution of hydrogen). After 15 min of stirring all the solvent was removed under reduced pressure to yield a black solid. This solid was dissolved with sodium hydroxide (3 M, 8 mL) and subsequently washed with hexanes (3.x.10 mL). The aqueous layer was then cooled to 0 °C (ice bath) and acidified to pH <=1 with concentrated HCl, with the boronic acid usually precipitating out as a white solid. The aqueous fraction was then extracted with diethyl ether (3.x.10 mL). The organic fractions were combined, dried with magnesium sulfate and filtered. The solvent was then removed under reduced pressure yielding a white solid.

Reference： [1] Tetrahedron, 2011, vol. 67, # 3, p. 576 - 583

5
[ 95-64-7 ]
[ 55499-43-9 ]

Yield	Reaction Conditions	Operation in experiment
73%	Stage #1: With hydrogenchloride; sodium nitrite In methanol; water at 0 - 5℃; for 0.5 h; Stage #2: With tetrahydroxydiboron In methanol; water at 20℃; for 1 h;	General procedure: To a solution of arylamine (0.5 mmol, 1.0 equiv) in MeOH(1.0 mL) was added HCl (0.5 mL, 1.5 mmol, 3.0 equiv), followed by H2O (0.5 ml). This mixture was stirred 2 min,and the NaNO2 solution (0.25 mL) was then added. The NaNO2 solution was prepared by dissolving 35 mg ofNaNO2 in H2O (0.25 mL). This mixture was stirred 30 minat 0–5 °C, followed by HCl (135 mg, 1.5 mmol, 3.0 equivalents) in MeOH (1.0 mL). This mixture was stirred 60min. H2O (10 mL) was added to reaction mixture, then extracted with CH2Cl2 (50 mL, 3×). The combined organic layer was dried over Na2SO4, followed by evaporation to give the products.

Reference： [1] Synlett, 2014, vol. 25, # 11, p. 1577 - 1584

6
[ 121-43-7 ]
[ 583-71-1 ]
[ 55499-43-9 ]

Reference： [1] Chemical Communications, 1998, # 9, p. 1047 - 1048

7
[ 583-71-1 ]
[ 55499-43-9 ]

Reference： [1] Angewandte Chemie - International Edition, 2008, vol. 47, # 6, p. 1115 - 1118
[2] ChemCatChem, 2018, vol. 10, # 19, p. 4253 - 4257

8
[ 5419-55-6 ]
[ 55499-43-9 ]

Reference： [1] ChemCatChem, 2018, vol. 10, # 19, p. 4253 - 4257

9
[ 16557-41-8 ]
[ 55499-43-9 ]

Reference： [1] Justus Liebigs Annalen der Chemie, 1901, vol. 315, p. 25

[ 55499-43-9 ] Synthesis Path-Downstream 1~88

1
[ 55499-43-9 ]
[ 88275-87-0 ]
[ 343603-59-8 ]

Reference： [1]Journal of Medicinal Chemistry,2002,vol. 45,p. 3573 - 3575
[2]Journal of Medicinal Chemistry,2002,vol. 45,p. 3576 - 3578

2
[ 34598-49-7 ]
[ 55499-43-9 ]
5-(3,4-dimethylphenyl)-2,3-dihydroinden-1-one [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2005,vol. 48,p. 5131 - 5139

3
[ 55499-43-9 ]
[ 17965-71-8 ]
C₁₆H₁₄N₂ [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2007,vol. 17,p. 6525 - 6528

4
5-chloro-1-(4-methoxybenzyl)-3-(phenylsulfanyl)pyrazin-2(1H)-one [ No CAS ]
[ 55499-43-9 ]
5-chloro-3-(3,4-dimethylphenyl)-1-(4-methoxybenzyl)-2(1H)-pyrazinone [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2007,vol. 5,p. 2962 - 2965

5
[ 234751-31-6 ]
[ 55499-43-9 ]
[ 234751-74-7 ]

Yield	Reaction Conditions	Operation in experiment
	With tetrabutylammomium bromide; sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In methanol; water; toluene; at 80℃; for 8h;	250 mg of 4-(3-bromophenyl)-6,7-dimethoxy-2-methylaminoquinazoline obtained in Production Example 8, 200 mg of 1,2-dimethyl-4-phenyl boric acid obtained from 4-bromo-o-xylene according to the method of J. Org. Chem., 56, 3763 (1991) and 50 mg tetrakis(triphenyl phosphine)palladium were suspended in a mixed solvent of 20 ml toluene, 5 ml methanol and 10 ml of 2 M aqueous sodium carbonate, and the mixture was stirred at 80 C. for 8 hours. The organic layer was recovered, washed with water twice and with brine, and then dried over anhydrous magnesium sulfate. The solvent was evaporated, and the crude product was purified and separated by silica gel column chromatography (hexane:ethyl acetate=1:1). The product was recrystallized from hexane-diisopropyl ether to give 186 mg of the title compound as pale yellow crystals. 1H-NMR (400 MHz, CDCl3) delta 2.31 (3H, s), 2.33 (3H, s), 3.14 (3H, d, J=4.8 Hz), 3.82 (3H, s), 4.04 (3H, s), 5.14 (1H,br s), 7.09 (1H, s), 7.16 (1H, s), 7.22 (1H, m), 7.39 (1H, m), 7.43 (1H, m) 7.58 (1H, t, J=7.6 Hz), 7.63 (1H, dt, J=7.6,1.6 Hz), 7.73 (1H, dt, J=7.6,1.6 Hz), 7.90 (1H, t, J=1.6 Hz). m.p. 149-151 C. MASS 400 (MH+)

Reference： [1]Patent: US6352989,2002,B1 .Location in patent: Page column 56

6
[ 54550-36-6 ]
[ 55499-43-9 ]
[ 725251-82-1 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium phosphate;bis(1,5-cyclooctadiene)nickel (0); bis(N-methylimidazol-2-yl)methane; In N,N-dimethyl acetamide; at 80℃; for 2h;	Examples 19 to 36 The process of Example 1 is repeated in a similar manner except that 0.40 mmol of boron compound as listed in Table 3 is used in place of p-methoxyphenylboronic acid and that 0.30 mmol of the organic halide compound as shown in Table 3 is used in place of 1-bromooctane, and each solvent as shown in Table 3 is used in place of N,N-dimethylacetamide, thereby the desired compounds as listed in Table 3 are obtained.

Reference： [1]Patent: EP1439157,2004,A2 .Location in patent: Page 12-16

7
methyl (2S)-2-((1S)-5-{2-[2-(4-bromophenyl)-1,4-dimethyl-1H-imidazol-5-yl]ethoxy}-2,3-dihydro-1H-inden-1-yl)propanoate [ No CAS ]
[ 55499-43-9 ]
methyl (2S)-2-((1S)-5-{2-[2-(3'-4'-dimethyl-1,1'-biphenyl-4-yl)-1,4-dimethyl-1H-imidazol-5-yl]ethoxy}-2,3-dihydro-1H-inden-1-yl)propanoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		To a mixture of 3, 4-dimethylphenyl boronic acid (17.0 mg, 0.11 [MMOL), METHYL] (2S) - [ 2- ( (1S)-5- {2- [2- (4-BROMOPHENYL)-1, 4-DIMETHYL-1H-IMIDAZOL-5-YL] ETHOXY} -2, 3-DIHYDRO-1 H-] inden-1-yl) propanoate (Example 139,28 mg, 0.06 [MMOL),] and Pd [(DPPF)] [CI2] (4.5 mg, 0.006 [MMOL)] was added toluene (2 mL) and dioxane (0.5 mL). The resulting solution was degassed under argon for half an hour, followed by addition of sodium bicarbonate solution (2 M, 0.5 mL), and then heated to [85C] for 16 h. The reaction mixture was allowed to cool to rt and diluted with 10 mL ethyl acetate. The organic layer was separated and passed through a 0.5 g silica plug. The combined organic layer was then concentrated under vacuum, leaving a dark brown oil, which was purified by HPLC with 10 to 80% acetonitrile in water to give 28.2 mg (95.6% yield) of desired [PRODUCT. 1H] NMR (CD30D) [8] 7.90 (d, 2 H), 7.73 (d, 2 H), 7.49 (s, 1 H), 7,43 (d, 1 H), 7.42 (d, 1 H), 6.98 (d, 1 H), 6.79 (s, [1] H), 6.70 (d, [1] H), 4.24 (t, 2 H), 3.91 (s, 3 H), 3.67 (s, 3 H), 3.43 (q, 1 H), 3.28 (t, 2 H), 2.71-2. 87 (m, 3 H), 2.36 (s, 3 H), 2.41 (s, 3 H), 2.32 (s, [3 H),] 2.09-2. 17 (m, [1] H), 1.83-1. 93 (m, 1 H), 1.02 (d, 3 H). [EL-LCMS] (rel abundance), [M/Z] 523.5 (MH+, 75%).

Reference： [1]Patent: WO2004/11446,2004,A1 .Location in patent: Page 128

8
[ 864086-51-1 ]
[ 55499-43-9 ]
7-(3,4-dimethylphenyl)-5H-dibenzo[c,g]chromene-3,9-diol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
26%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In DMF (N,N-dimethyl-formamide); water; at 120℃; for 1h;	Example 39; 7- (3, 4-Dimethylphenyl)-5H-dibenzo [c, g] chromene-3, 9-diol [0083]; To a mixture of 7-bromo-H-dibenzo [c, g] chromene-3,9-diol (343 mg, 1 mmol), dimethylformamide (5 mL), 2 M sodium carbonate (1 mL), water (1 mL), and tetrakis (triphenylphosphine) palladium (116 mg, 0.1 mmol) was added 3,4- dimethylphenylboronic acid (450 mg, 3 mmol). The reaction mixture was heated to 120 C for 1 hr, then cooled and diluted with ethyl acetate (25 mL) and 5% ammonium chloride. The organic layer was washed with water (3 x 10 mL) and brine (10 mL) and dried over anhydrous magnesium sulfate. The solvent was removed and the resulting tan solid was purified by chromatography (2. 5% acetonitrile-dichloromethane) to afford a white solid (95 mg, 26%) : mp 218-221 C ; 1H NMR (DMSO-d6) : 8 2.29 (3H, s), 2.31 (3H, s) 4.92 (2H, s), 6.62-6. 65 (2H, m), 6.82-6. 91 (2H, m), 7.01-7. 05 (1H, m), 7.08 (1H, s), 7.25 (1H, d, J=7. 7 Hz), 7.77-7. 83 (2H, m), 8.16 (1H, s), 9.48 (1H, s), 9.70 (1H, s); MS mlz 369 ( [M+H] +). An. HPLC gave purity of 97. 3% 280 nm. Anal. for C25H2oO3-O. 2 H2O : Calc'd: C: 80.71 ; H: 5.53 Found: C: 80.61 ; H: 5.43

Reference： [1]Patent: WO2005/82880,2005,A1 .Location in patent: Page/Page column 37

9
[ 879875-66-8 ]
[ 55499-43-9 ]
C₃₄H₄₅NO₃Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate; lithium chloride;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; for 3h;Heating / reflux;	A mixture of the enol triflate 3 (250 mg, 0.425 mmol), 3,4-dimethylphenylboronic acid 5a (0.47 mmol), tetrakis (triphenylphosphine)-palladium(0) (9.8 mg, 0.0085 mmol), lithium chloride (54 mg, 1.275 mmol) and a 2N aqueous solution of sodium carbonate (0.64 ml, 1.275 mmol) in 10 mL of DME was refluxed under N2 for 3 h. The mixture was cooled to 0 C., water (30 mL) was added, and the mixture was extracted with Ethyl acetate. The combined organic extracts were washed with water, brine and dried over MgSO4. The mixture was filtered and the filtrate was evaporated under reduced pressure. The crude product 6a was used for the next step without further purification.

Reference： [1]Patent: US2006/63792,2006,A1 .Location in patent: Page/Page column 22; 35

10
[ 613660-78-9 ]
[ 55499-43-9 ]
[ 613660-98-3 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate; trifluoroacetic acid;tetrakis(triphenylphosphine)palladium (0); In methanol; diethyl ether; dichloromethane; water; acetonitrile;	EXAMPLE 40 3-(3,4-dimethylphenyl)-5-[(2-methylpyrrolidin-1-yl)carbonyl]pyridine A solution of Example 30 (1 mmol), (3,4-dimethyl)phenylboronic acid (2.0 mmol), and tetrakis(triphenylphosphine)palladium (0) (0.05 mmol) in dichloromethane (1.5 mL) and methanol (0.25 mL) is treated with 2M sodium carbonate (0.5 mL), heated to 87 C. overnight, and concentrated. The concentrate is dissolved in diethyl ether, washed three times with water, dried (Na2SO4), filtered, and concentrated. The concentrate is purified by HPLC using a C-18 column and a solvent system increasing in gradient over 50 minutes from 5% to 100% acetonitrile/water containing 0.01% TFA and lyophilized to provide the desired product as the trifluoroacetate salt.

Reference： [1]Patent: US2003/195192,2003,A1

11
[ 55499-43-9 ]
[ 152941-67-8 ]
2-amino-4-isopropoxy-6-(3,4-dimethylphenyl)-pyrido[2,3-d]pyrimidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
42%		Example 38 - synthesis of 2-amino-4-isopropoxy-6-(3,4-dimethylphenvO-pyridor2,3- cyipyrimidine; A similar procedure as in example 2 was followed. To a solution of 2- pivaloylamino-4-isopropoxy-6-bromo-pyrido[2,3-d]pyrirnidine (0.5 mmole) in tetrahydrofuran (15 ml) was added <strong>[55499-43-9]3,4-dimethylphenyl boronic acid</strong> (0.5 mmole), tetrakis(triphenylphosphine)palladium(0) (0.025 mmole) and 15 ml of a 0.4 M Na2CO3 aqueous solution. The reaction mixture was refluxed at 95 0C for 30 minutes, yielding crude 2-pivaloylamino-4-isopropoxy-6-(3,4-dimethylphenyl)-pyrido[2,3-o(]pyrimidine which was resuspended in a mixture of methanol (7 ml) and a 20 % K2CO3 aqueous solution (7 ml). The reaction mixture was refluxed for 2 hours, after which no pivaloylated material could be observed on thin layer chromatography. The solvents were evaporated in vacuo and the residue was purified by silica gel column chromatography, the mobile phase consisting of a CH3OH/CH2CI2 mixture in a ratio of 1 :35, resulting in the title compound as a pure white powder (65 mg, yield 42 %) which was characterized by its mass spectrum and its ultraviolet light spectrum as follows:- MS (m/z) : 309 ([M+H]+, 100), and- UV : 218, 242, 287 and 357 nm.

Reference： [1]Patent: WO2006/87229,2006,A1 .Location in patent: Page/Page column 53

12
[ 908138-10-3 ]
[ 55499-43-9 ]
4-(3,4-dimethyl-phenyl)-7-trifluoromethyl-quinoline-3-carboxylic acid ethyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium phosphate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; at 80℃;	4-Trifluoromethanesulfonyloxy-7-trifluoromethyl-quinoline-3-carboxylic acid ethyl ester (208 mg, 0.5 mmol), 3,4-dimethylphenylboronic acid (82.5 mg, 0.55 mmol), tetrakis(triphenylphosphine)palladium(0) (29 mg) and potassium phosphate (159 mg, 0.75 mmol) were heated together in dioxane (5 mL) to 80C overnight. The reaction mixture was then diluted with ethyl acetate and washed with brine twice. The organic layer was dried over sodium sulfate, concentrated, and the residue purified by flash column eluted with 30% ethyl acetate in hexane to yield 4-(3,4-dimethyl-phenyl)-7-trifluoromethyl-quinoline-3- carboxylic acid ethyl ester as a slight yellow oil. LCMS: 4.115 min, m/z: 374 (M + 1 ).
	With potassium phosphate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; at 80℃;	4-Trifluoromethanesulfonyloxy-7-trifluoromethyl-quinoline-3-carboxylic acid ethyl ester (208 mg, 0.5 mmol), 3,4-dimethylphenylboronic acid (82.5 mg, 0.55 mmol), tetrakis(triphenylphosphine)palladium(0) (29 mg) and potassium phosphate (159 mg, 0.75 mmol) were heated together in dioxane (5 mL) to 8O0C overnight. The reaction mixture was then diluted with ethyl acetate and washed with brine twice. The organic layer was dried over sodium sulfate, concentrated, and the residue purified by flash column eluted with 30% ethyl EPO <DP n="38"/>acetate in hexane to yield 4-(3,4-dimethyl-phenyl)-7-trifluoromethyl-quinoline-3- carboxylic acid ethyl ester as a slight yellow oil. LCMS: 4.115 min, m/z: 374 (M + 1 ).

Reference： [1]Patent: WO2006/91769,2006,A1 .Location in patent: Page/Page column 37
[2]Patent: WO2006/91800,2006,A2 .Location in patent: Page/Page column 36-37

13
[ 350601-39-7 ]
[ 55499-43-9 ]
[ 7688-25-7 ]
[ 496850-10-3 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; cesium fluoride;palladium diacetate; In hexane; water; ethyl acetate; acetonitrile;	25. Preparation of Methyl 4-amino-3-chloro-6-(3,4-dimethylphenyl)pyidine-2-carboxylate (Compound 12) A solution of 3,4-dimethylphenylboronic acid (2.1 g, 14.0 mmol), cesium fluoride (6.3 g, 41.5 mmol), 1,4-bis(diphenylphosphino)butane (0.5 g, 1.2 mmol), methyl 4-amino-3,6-dichloropyridine-2-carboxylate (2.5 g, 10.0 mmol) and triethylamine (5 mL) in acetonitrile (100 mL) was sparged for thirty minutes with nitrogen. Palladium acetate (0.3 g, 1.2 mmol) was added and the reaction mixture heated under reflux for three hours. After cooling water (200 mL) was added and the mixture extracted with ethyl acetate (2*100 mL). The organic layer was washed with brine (100 mL), dried (NaSO4), and concentrated. The residue was purified by column chromatography (33 percent ethyl acetate in hexane) to give methyl 4-amino-3-chloro-6-(3,4-dimethylphenyl)pyridine-2-carboxylate (1.4 g, 5.0 mmol), mp 154-156 C. The following 4-amino-6-(aryl or heteroaryl)picolinates were prepared according to the procedure of Example 25:

Reference： [1]Patent: US2003/114311,2003,A1

14
[ 586-76-5 ]
[ 55499-43-9 ]
[ 122294-09-1 ]

Yield	Reaction Conditions	Operation in experiment
77%		3,4 - Dimethylphenylboronic acid (6.4 g, 42.7 mmol), 4-bromobenzoic acid (10.5g,52.7 mmol) sodium carbonate (13.6 g, 128.3 mmol) and tetrakis(triphenylphosphine)palladium (0) (1.2 g, 1.0 mmol) in dimethoxyethane (90 mL)/ water (30 mL) were refluxed for 5 h then concentrated. The residue was carefully treated with 1 N HCI and extracted into ethyl acetate.The extract was washed with brine, dried (MgSO4) and concentrated to a light orange solid EPO <DP n="56"/>(11.4 g). Recrystallization from ethanol gave 7.4 g (77% - 2 crops) of -95% pure 3',4'- dimethyl-biphenyl-4-carboxylic acid as a white solid which had: mp 211-2130C; NMR (CDCI3) delta 12.94 (s, 1 H), 7.97 (d, J = 8.3 Hz, 2H), 7.74 (d, J = 8.3 Hz, 2H), 7.51 (d, J = 1.2 Hz, 1H), 7.43 (dd, J = 7.9, 2.1 Hz, 1 H), 7.23 (d, J = 7.9 Hz, 1H), 2.28 (s, 3H), 2.24 (s, 3H).

Reference： [1]Patent: WO2007/34277,2007,A1 .Location in patent: Page/Page column 54-55

15
[ 335242-55-2 ]
[ 55499-43-9 ]
3-(3,4-dimethyl-benzoyl)-1H-cinnolin-4-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate;bis-triphenylphosphine-palladium(II) chloride; In methoxybenzene; at 150℃; for 3h;	1.49 g (6.61 mmol) of 3 -bromo-1 H-cinnolin-4-one 7a (Prepared as described in U S Patent 4,379,929), 2.48 g (16.5 mmol) of 3,4-dimethylrhohenylboronic acid, 4.57 g (33.1 mmol) of potassium carbonate and 464 mg (0.661 mmol) of bis(triphenylphosrhohine)rhoalladium(II) di chloride were stirred in 50 mL of anisole at 150 C under the atmosphere of carbon monoxide for 3 h. The mixture was cooled down, filtered and concentrated in vacuo. Flash chromatography of the crude product 8a using 10-80% ethyl acetate in hexane to give 78 mg of the product as off-white solid: LC-MSD, m/z for Ci7Hi4N2O2 [M+H]+ = 279.1, HPLC retention time: 1.9 min.

Reference： [1]Patent: WO2007/59108,2007,A2 .Location in patent: Page/Page column 55

16
[ 1015075-33-8 ]
[ 55499-43-9 ]
[ 1015075-59-8 ]

Reference： [1]Journal of Organic Chemistry,2008,vol. 73,p. 2382 - 2388

17
[ 76334-36-6 ]
[ 55499-43-9 ]
[ 1134201-59-4 ]

Reference： [1]Journal of the American Chemical Society,2009,vol. 131,p. 4136 - 4142

18
[ 1235467-34-1 ]
[ 55499-43-9 ]
[ 1235467-35-2 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; at 105℃; for 4h;Microwave irradiation;	5-Bromo-2-(4-(morpholine-4-carbonyl)phenylamino)benzonitrile (300 mg, 0.777 mmol), Pd(Ph3P)4 (44.9 mg, 0.039 mmol), aqueous 2M Na2CO3 (0.882 mL, 1.763 mmol) were mixed with toluene (4 mL) in a sealed microwave tube. 3,4- dimethylphenylboronic acid (163 mg, 1.087 mmol) in MeOH (2.00 mL) was added to the above mixture. The mixture was heated at 105 C for 4hrs in an oil bath. The crude was diluted with CH2CI2 (100ml) and washed with water (2X50ml), brine, dried with MgStheta4 and concentrated. 378mg of crude product (77% purity) was obtained and it will be used as it is.

Reference： [1]Patent: WO2010/80474,2010,A1 .Location in patent: Page/Page column 129

19
[ 1233696-82-6 ]
[ 55499-43-9 ]
[ 1233696-84-8 ]

Yield	Reaction Conditions	Operation in experiment
95%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; at 100℃; for 16h;Inert atmosphere;	A vial was charged with methyl 7-(4-(6- bromopyridin-2-ylcarbamoyl)phenoxy)-6-cyanochroman-4-carboxylate (51 mg, 0.100 mmol), 3,4-dimethylphenylboronic acid (19.5 mg, 0.130 mmol), Na2CO3 (31.9 mg, 0.300 mmol), toluene (1 mL) and water (0.1 mL). The mixture was degassed with Argon for few minutes, and then Pd(PPh3)4 (5.8 mg, 0.005 mmol) was added. The vial was sealed and heated at 1000C for 16 hours. The reaction was cooled and the crude material was purified by silica gel column chromatography to provide the desired product (0.051 g, 95%).

Reference： [1]Patent: WO2010/75200,2010,A1 .Location in patent: Page/Page column 69

20
[ 557-21-1 ]
[ 55499-43-9 ]
[ 22884-95-3 ]

Reference： [1]Journal of the American Chemical Society,2010,vol. 132,p. 11389 - 11391

21
[ 1256254-43-9 ]
[ 55499-43-9 ]
[ 1256254-52-0 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;bis-triphenylphosphine-palladium(II) chloride; In N,N-dimethyl-formamide; at 110℃; for 16h;Inert atmosphere; Sealed tube;	Step 1 : To a solution of the dichloropyridine 2h (Example 2) (2.0 g, 6.25 mmol) and 3,4- dimethylphenylboronic acid 4a (1.12 g, 7.5 mmol) in DMF (20 mL) is added 2M Na2CO3 (7.8 mL, 16 mmol) followed by PdCI2(PPh3)2 (440 mg, 0.62 mmol). The reaction mixture is degassed by bubbling with argon (10 min), the reaction vessel is sealed and the mixture is heated at 1 10C for 16 h. The cooled mixture is diluted with EtOAc, washed with water and brine, dried over MgSO4 and filtered. The residue is purified by CombiFlash Companion (Hexanes/EtOAc) to give 4b

Reference： [1]Patent: WO2010/130034,2010,A1 .Location in patent: Page/Page column 50

22
[ 255837-23-1 ]
[ 55499-43-9 ]

Yield	Reaction Conditions	Operation in experiment
85%		General procedure: Triphenylphosphene (0.131 g, 0.5 mmol, 20 mol %), p-iodoanisol (0.585 g, 2.5 mmol), and triethylamine (1.78 mL, 12.5 mmol) were added to a 50 mL round-bottomed flask equipped with a sidearm, condenser, and stir bar. This solution was then degassed by alternating vacuum and argon three times. Palladium dichloride (0.023 g, 0.13 mmol, 5 mol %) was then added under positive argon pressure. After stirring at room temperature for 15 min, diisopropylaminoborane (5 mL, 1 M solution in THF, 5 mmol) was added and the reaction mixture was degassed again by alternating vacuum and argon three times. The reaction solution was then heated to reflux. After 12 h of reflux the reaction was cooled to 0 C and 6 mL of methanol was added through the condenser slowly (Caution: exothermic reaction with evolution of hydrogen). After 15 min of stirring all the solvent was removed under reduced pressure to yield a black solid. This solid was dissolved with sodium hydroxide (3 M, 8 mL) and subsequently washed with hexanes (3×10 mL). The aqueous layer was then cooled to 0 C (ice bath) and acidified to pH ?1 with concentrated HCl, with the boronic acid usually precipitating out as a white solid. The aqueous fraction was then extracted with diethyl ether (3×10 mL). The organic fractions were combined, dried with magnesium sulfate and filtered. The solvent was then removed under reduced pressure yielding a white solid.

Reference： [1]Tetrahedron,2011,vol. 67,p. 576 - 583

23
[ 59489-71-3 ]
[ 55499-43-9 ]
[ 1354652-73-5 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 110℃; for 4.5h;	Intermediate Id: 5-(3,4-dimethylphenyl pyrazin-2-amine.; To a solution of 5- bromopyrazin-2-amine (4 g, 22.99 mmol, 1.00 equiv) in 1,4-dioxane (68 mL) and methanol (23 mL) was added 3,4-dimethylphenylboronic acid (3.52 g, 23.47 mmol, 1.02 equiv), sodium carbonate (4.872 g, 45.96 mmol, 2.00 equiv) in water (23 mL), and Pd(PPh3)4 (532 mg, 0.46 mmol, 0.02 equiv) and the resulting solution was stirred for 4.5 h at 110C in an oil bath. The resulting mixture was concentrated under vacuum, diluted with 200 mL of ethyl acetate, washed with 2x100 mL of brine, dried over anhydrous sodium sulfate and then concentrated under vacuum. The residue was applied onto a silica gel column with petroleum ether/ethyl acetate=10:l~l :l, then with dichloromethane/methanol (10: 1-5:1). The collected fractions were combined and concentrated under vacuum. This resulted in 4.82 g (crude) of 5-(3,4- dimethylphenyl)pyrazin-2-amine as a yellow solid.

Reference： [1]Patent: WO2012/6474,2012,A2 .Location in patent: Page/Page column 46

24
[ 7752-82-1 ]
[ 55499-43-9 ]
[ 1111101-85-9 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 100℃;Inert atmosphere;	Intermediate 7b: 5-(3,4-dimethylphenyl)pyrimidin-2-amine.; Into a 250-mL 3-necked round bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed 5-bromopyrimidin-2-amine (5 g, 28.74 mmol, 1.00 equiv), 3,4- dimethylphenylboronic acid (4.4 g, 29.33 mmol, 1.00 equiv), dioxane (85 mL), methanol (29 mL), sodium carbonate(6.1 g, 57.55 mmol, 2.00 equiv) in water (29 mL), and Pd(PPh3)4 (664 mg, 0.57 mmol, 0.02 equiv). The resulting solution was stirred overnight at 100C in an oil bath. The mixture was concentrated under vacuum. The residue was applied onto a silica gel column and eluted with dichloromethane:methanol (50:1). This resulted in 6 g (crude) of 5-(3,4- dimethylphenyl)pyrimidin-2-amine as a yellow solid.

Reference： [1]Patent: WO2012/6474,2012,A2 .Location in patent: Page/Page column 66-67

25
[ 55499-43-9 ]
[ 15862-47-2 ]
[ 1246029-39-9 ]

Yield	Reaction Conditions	Operation in experiment
68%	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; N,N-dimethyl-formamide; at 50 - 85℃; for 12h;	At 50 C., 4.5 g (16.2 mmol) of N-(5-bromopyridin-3-yl)benzamide, 3.0 g (19.5 mmol) of <strong>[55499-43-9](3,4-dimethylphenyl)boronic acid</strong> and 4.5 g (32.5 mmol) of potassium carbonate were dissolved in 59 ml of 1,2-dimethoxyethane, 19 ml of water and 117 ml of DMF. The mixture was flushed with argon, 0.1 g (0.08 mmol) of tetrakis(triphenylphosphine)palladium(0) was added and the mixture was stirred at 85 C. for 12 h. The reaction mixture was concentrated slightly on a rotary evaporator, diluted with water and extracted with dichloromethane. The organic phase was concentrated and purified by column chromatography on silica gel (dichloromethane/methanol 100:1?100:4).Yield: 3.4 g (68% of theory)LC-MS (Method 2B): Rt=1.17 min; m/z=303 [M+H]+.

Reference： [1]Patent: US2012/46268,2012,A1 .Location in patent: Page/Page column 28

26
[ 1364596-18-8 ]
[ 55499-43-9 ]
[ 76-05-1 ]
methyl 2-tert-butoxy-2-(7-(3,4-dimethylphenyl)-5-methyl-2-phenylpyrazolo[1,5-a]pyrimidin-6-yl)acetate trifluoroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
54.3%		Methyl 2-tert-butoxy-2-(7-(3, 4-dimethylphenyl)-5-methyl-2-phenylpyrazolo[ 1, 5- a]pyrimidin-6-yl)acetate, TFA salt.; To a 0.5-2 mL microwave tube was added methyl 2-tert-butoxy-2-(7-chloro-5-methyl-2-phenylpyrazolo[l,5-a]pyrimidin-6- yl)acetate (20 mg, 0.052 mmol), tetrakis(triphenylphosphine)palladium(0) (8.94 mg, 7.73 muiotaetaomicron), 3,4-dimethylphenylboronic acid (11.60 mg, 0.077 mmol), DMF (1.5 mL), followed by 2M K3PO4 8thetaGammaiotaomicroneta(100muiota). The reaction mixture was heated in a microwave reactor at 130C for 15min. The reaction mixture was filtered and the filtrate purified by preparative HPLC to afford (16mg, 54.3%) of the title compound as TFA salt. Preparative HPLC condition: Phenomenex Luna CI 8 30 x 100mm S10, 50 to 100% B over 22 minute gradient, 8 minute hold time, A = 10% methanol 90% water 0.1% TFA, B = 90% methanol 10% water 0.1% TFA. Flow rate: 40ml/min. ¾-NMR (300 MHz, CDCh, 60C) delta ppm 0.97 (9 H, s), 2.34 (3 H, s), 2.39 (3 H, s), 2.74 (3 H, s), 3.78 (3 H, s), 5.14 (1 H, s), 7.00 (1 H, s), 7.27 - 7.48 (6 H, m), 7.82 (2 H, dd, J=7.9, 1.6 Hz).

Reference： [1]Patent: WO2012/33735,2012,A1 .Location in patent: Page/Page column 44-45

27
[ 1365943-11-8 ]
[ 55499-43-9 ]
[ 1365943-59-4 ]

Yield	Reaction Conditions	Operation in experiment
	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium phosphate; In 1,4-dioxane; water; at 95℃; for 24h;Inert atmosphere;	General procedure: To an array of vials containing a solution of aryl triflate 10 (30 mg, 1 equiv) in 1,4-dioxane (1 mL)was added various aryl boronic acids (1.1 equiv), [1,10-bis(diphenylphosphino)ferrocene] dichloropalladium(II) (0.03 equiv) and aqueous K3PO4 (3 equiv). The reaction mixtures were degassed with nitrogen and heated at 95 C for 24 h. The reaction mixtures were cooled to room temperature and were filtered through a short pad of silica. The filtrates were evaporated in a Genevac. To the resulting array of crude aldehyde was added a suspension of sodium borohydride (1 equiv) in anhydrous ethanol (1 mL). The reaction mixtures were stirred at room temperature for 4 h. The solvents were evaporated in a Genevac and the residues were purified by reverse phase preparative HPLC.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2012,vol. 22,p. 2287 - 2290

28
[ 1372606-92-2 ]
[ 55499-43-9 ]
[ 1372605-58-7 ]

Yield	Reaction Conditions	Operation in experiment
65%	With sodium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In water; toluene; at 90℃; for 2h;Inert atmosphere;	Example 38 Preparation of N-(5-(3,4-dimethylphenyl)-6-(2,2,2-trifluoroethoxy)pyridin-3-yl)nicotinamide In a 25 mL sealed tube N-(5-bromo-6-(2,2,2-trifluoroethoxy)pyridin-3-yl)nicotinamide (200 mg, 532 mumol) was combined with toluene (11 mL). Under argon atmosphere, were added 3.4-dimethylbenzeneboronic acid (160 mg, 1.06 mmol), an aqueous solution of sodium carbonate (2M, 0.53 mL) and Pd(dppf)2Cl2 (12 mg, 0.016 mmol). After two hours at 90 C., the dark red suspension was cooled to room temperature, diluted with ethyl acetate (10 mL), and washed with water (10 mL) and brine (10 mL). The aqueous layer was back-extracted with ethyl acetate (15 mL). The organic layers were dried over MgSO4 and concentrated in vacuo. Crystallization from ethyl acetate/heptane (5 mL, 1/2) gave a white solid (96 mg), the filtrate was evaporated to dryness and purified by column chromatography (silica gel, 20 g, 10% to 100% ethyl acetate in heptane) to get a second part of the desired product as a white solid (139 mg).
65%	With sodium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In water; toluene; at 90℃; for 2h;Inert atmosphere;	Example 38Preparation of N-(5-(3,4-dimethylphenyl)-6-(2,2,2-trifluoroethoxy)pyridin-3-yl)nicotinamideIn a 25 mL sealed tube N-(5-bromo-6-(2,2,2-trifluoroethoxy)pyridin-3-yl)nicotinamide (200 mg, 532 muiotaetaomicron) was combined with toluene (11 mL). Under argon atmosphere, were added 3.4-dimethylbenzeneboronic acid (160 mg, 1.06 mmol), an aqueous solution of sodium carbonate (2M, 0.53 mL) and Pd(dppf)2Cl2 (12 mg, 0.016 mmol). After two hours at 90 C, the dark red suspension was cooled to room temperature, diluted with ethyl acetate (10 mL), and washed with water (10 mL) and brine (10 mL). The aqueous layer was back-extracted with ethyl acetate (15 mL). The organic layers were dried over MgS04 and concentrated in vacuo.Crystallization from ethyl acetate / heptane (5 mL, 1 / 2) gave a white solid (96 mg), the filtrate was evaporated to dryness and purified by column chromatography (silica gel, 20 g, 10% to 100% ethyl acetate in heptane) to get a second part of the desired product as a white solid (139 mg). Overall yield was 65%; MS (EI): 402.3 (M+H).

Reference： [1]Patent: US2012/94993,2012,A1 .Location in patent: Page/Page column 26
[2]Patent: WO2012/49190,2012,A1 .Location in patent: Page/Page column 59-60

29
[ 1380347-01-2 ]
[ 55499-43-9 ]
[ 1380347-61-4 ]

Yield	Reaction Conditions	Operation in experiment
87%	With palladium diacetate; sodium carbonate; (S)-(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine); In 1,2-dimethoxyethane; water; at 80℃; for 15h;Inert atmosphere;	To a stirred solution of 25 (330 mg, 0.579 mmol) in DME (4 mL) and 2 M aqueous sodium carbonate (0.87 mL, 1.74 mmol) were added 2,4-dimethylphenylboronic acid (173 mg, 1.15 mmol), (S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) (72 mg, 0.116 mmol) and palladium acetate (13 mg, 0.058 mmol) under argon atmosphere. After being stirred at 80 C for 15 h, the reaction mixture was cooled to room temperature. The resulting mixture was filtered through a pad of Celite, and the filtrate was evaporated. The resulting residue was purified by column chromatography on silica gel (hexane/EtOAc, 4:1-1:1) to afford 26a as a brown oil (321 mg, 93%). 1H NMR (300 MHz, CDCl3): delta 7.27 (s, 1H), 7.15-7.00 (m, 6H), 5.65 (m, 1H), 5.46 (m, 1H), 4.43 (m, 1H), 4.30 (m, 1H), 4.17-4.02 (m, 3H), 2.80-2.71 (m, 2H), 2.35 (s, 3H), 2.33-2.22 (m, 2H), 2.23 (s, 3H), 1.86-1.68 (m, 2H), 1.41 (s, 9H), 1.25 (t, J = 7.0 Hz, 3H), 0.79 (s, 9H), -0.13 (s, 3H), -0.24 (s, 3H).

Reference： [1]Bioorganic and Medicinal Chemistry,2012,vol. 20,p. 3502 - 3522

30
[ 1392119-18-4 ]
[ 55499-43-9 ]
[ 1392119-19-5 ]

Yield	Reaction Conditions	Operation in experiment
62%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In N,N-dimethyl-formamide; at 120℃; for 0.333333h;Inert atmosphere; Microwave irradiation;	Step D(R)-3-(2-((tert-butyldiphenylsilyl)oxy)-1-hydroxyethyl)-4-(3,4-dimethylphone[00153] A solution of 4-bromo-3-((1 R)-2-[(1 , 1 -dimethylethyl)(diphenyl)silyl]oxy}-1- hydroxyethyl)-1 H-2-benzopyran-1-one (142 mg, 0.271 mmol) and 3,4-dimethylphenylboronic acid (61.0 mg, 0.407 mmol) in Nu,Nu-Dimethylformamide (DMF) (2.5 mL) was degassed with N2 for 10 min. The reaction mixture was treated with 2M Na2C03 (149 muIota, 0.298 mmol) and Pd(PPh3)4 (16 mg, 0.014 mmol) and irradiated in the microwave for 20 min at 120 C. The reaction mixture was diluted with EtOAc, and washed with saturated aqueous NH4CI, brine, dried (Na2S04), filtered and concentrated. The residue was purified by silica gelchromatography (ethyl acetate-hexanes 0-30%) to afford the title compound (92 mg, 0.168 mmol, 62 % yield) as a white solid: Rt = 1.31 , 1 .33 (atropisomers), ES+ MS: 571 (M + 23).

Reference： [1]Patent: WO2012/102985,2012,A1 .Location in patent: Page/Page column 107

31
[ 1417464-13-1 ]
[ 55499-43-9 ]
[ 1417464-15-3 ]

Yield	Reaction Conditions	Operation in experiment
79%	With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; at 90℃; for 4h;	General procedure: 3.5.3 2,3,5,6-Tetrakis(3,4-dimethylphenyl)cyclohexa-2,5-diene-1,4-dione (3s) Starting from 5 (211 mg, 0.5 mmol), and 2r (300 mg, 2.0 mmol) following general procedure D, 3s was obtained as a yellow solid (207 mg, 79%), mp=224-226 C; 1H NMR (300 MHz, 298 K, CDCl3): delta=2.06, 2.10 (s, 24H, 8CH3), 6.69 (d, 4H, 3J=7.8 Hz, HAr), 6.85 (m, 8H, HAr); 13C NMR (75 MHz, 298 K, CDCl3): delta=19.6, 19.7 (CH3), 128.2 (CAr), 128.9 (CHAr), 130.5 (CAr), 132.1, 135.5 (CHAr), 136.6, 142.6 (CAr), 187.5 (C=O); IR (neat, cm-1): =3260, 3019 (w), 2915 (m), 2728 (w), 1645 (s), 1607, 1557, 1495, 1446, 1379, 1313, 1223, 1177, 1111, 1068, 1019 (m), 958 (w), 896 (m), 814 (s), 758, 717, 659, 575 (m) cm-1.

Reference： [1]Tetrahedron,2013,vol. 69,p. 460 - 469

32
[ 1373433-13-6 ]
[ 55499-43-9 ]
[ 1400664-39-2 ]

Yield	Reaction Conditions	Operation in experiment
54%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In methanol; water; toluene; for 2h;Reflux;	General procedure: To a solution of 2-chloro-6-[3-methoxy-4-[2-(pyrrolidin-1-yl)ethoxy]phenyl]-5H-pyrrolo[3,4-b]pyridin-7(6H)-one (70 mg, 0.18 mmol) and phenylboronic acid (44 mg, 0.36 mmol) in toluene and methanol (4:1, 5 ml) were added tetrakis(triphenylphosphine palladium (20 mg, 0.018 mmol) and sodium carbonate (0.18 ml, 0.54 mmol, 2M in H2O), then the mixture was refluxed for 2 h. After completion of reaction, the reaction mixture was combined with 20 ml of water and extracted with dichoromethane (20 ml x 2) being washed with water and brine. The combined organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was refined by silica gel column chromatography (10% MeOH/CH2Cl2) to give 52 mg (yield 67%) of the title compound.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 1736 - 1739

33
C₁₈H₁₆F₃N₃O₇S [ No CAS ]
[ 55499-43-9 ]
[ 1428795-28-1 ]

Yield	Reaction Conditions	Operation in experiment
645 mg	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,4-dioxane; water; at 70℃; for 1h;Inert atmosphere;	OO e To a solution of methyl 4-hydroxy-1 -(4-methoxybenzyl)-6-methyl-7-oxo-6,7-dihydro-1 H- pyrazolo[3,4-c]pyridine-5-carboxylate (585 mg, 1.7 mmol) in dichloromethane (15 mL) was added TEA (0.48 mL, 3.4 mmol) and the mixture was cooled to 0C and triflic anhydride (0.32 mL, 1 .87 mmol) was added dropwise. After 1 h the mixture was washed with saturated sodium bicarbonate/water and brine. The organic phase was dried over sodium sulfate and concentrated. To a solution of crude triflate in 1 ,4-dioxane (14 mL) was added (3,4- dimethylphenyl)boronic acid (0.33 g, 2.2 mmol), Palladium tetrakis (0.19 g, 0.17 mmol) and a solution of sodium carbonate (0.54 g, 5.05 mmol) in water (3.5 mL) and the mixture was heated to 70C under nitrogen atmosphere for 1 h. EtOAc and water was added and the mixture was washed with saturated sodium bicarbonate/water. The organic phase was dried over sodium sulfate, concentrated and purified on silica using EtOAc/hexanes 0-30% to provide the title compound (645 mg, 84%). 1H NMR (400MHz, DMSO-d6) delta ppm 7.65 (s, 1 H), 7.4 (d, 2H), 7.2 (d, 1 H), 7.14 (s, 1 H), 7.08 (d, 1 H), 6.85 (d, 2H), 5.92 (s, 2H), 3.8 (s, 3H), 3.64 (s, 3H), 3.6 (s, 3H), 2.28 (s, 3H), 2.26 (s, 3H); ES-LCMS: 432.24 (M+1 ).

Reference： [1]Patent: WO2013/43553,2013,A1 .Location in patent: Page/Page column 147-148

34
[ 1217-89-6 ]
[ 55499-43-9 ]
C₂₃H₂₁NO₂ [ No CAS ]
C₂₃H₂₁NO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With C57H70NOP; palladium diacetate; beta-naphthol; potassium hydroxide; In tetrahydrofuran; at 20℃; for 48h;	General procedure: A solution of Pd (OAc)2 (2.25 mg, 0.01 mmol) and (Sa,S)-8g(9.78 mg, 0.012 mmol) in THF (1.0 mL) was stirred for 30 min atroom temperature. KOH (11.2 mg, 0.2 mmol), isatins (0.20 mmol),arylboronic acids (0.4 mmol) and additives (0.03 mmol) were addedsuccessively with additional THF (1.0 mL). The resulting mixturewas stirred for 48 h at room temperature. Then the solvent wasremoved under vacuum and the residue was purified by flash columnchromatography using silica gel with ethyl acetate/petroleumether as eluent.

Reference： [1]Applied Catalysis A: General,2013,vol. 458,p. 201 - 206

35
[ 1395347-62-2 ]
[ 55499-43-9 ]
[ 1447249-85-5 ]

Reference： [1]Organic and Biomolecular Chemistry,2013,vol. 11,p. 4778 - 4791

36
[ 55499-43-9 ]
[ 87639-57-4 ]
[ 1371598-36-5 ]

Yield	Reaction Conditions	Operation in experiment
90%	With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In methanol; toluene; at 80℃; for 4h;Inert atmosphere;	Example 2-1 Synthesis of 3,4-dimethylbiphenyl-3',4'-dicarboxylic acid dimethyl ester (method (B) 24.1 g (88 mmol) of dimethyl 4-bromophthalate, 14.5 g (97 mmol) of 3,4-dimethylphenylboronic acid, and 24.4 g (176 mmol) of potassium carbonate were added to a 500-mL three-necked round-bottom flask equipped with a stirrer, a thermometer and a reflux condenser tube, and the inside of the reaction system was maintained under an argon atmosphere. Subsequently, 270 mL of toluene, 30 mL of methanol, and 3.1 g (4.4 mmol) of dichlorobis(triphenylphosphine)palladium were added to the reaction system, and the obtained mixture was then reacted at 80 C. for 4 hours, while stirring. After completion of the reaction, the reaction solution was cooled to a room temperature, and it was then filtrated with Celite. The filtrate was purified by silica gel column chromatography, and the obtained crude product was then dissolved in 100 mL of hot methanol to precipitate a crystal, to obtain 23.6 g of 3,4-dimethylbiphenyl-3',4'-dicarboxylic acid dimethyl ester in the form of a white solid (isolation yield: 90%). The obtained 3,4-dimethylbiphenyl-3',4'-dicarboxylic acid dimethyl ester is a novel compound having the following physical properties.Melting point: 92 C. to 94 C. [0060] 1H-NMR (300 MHz, CDCl3 (delta (ppm)); 2.31 (s, 3H), 2.33 (s, 3H), 3.92 (s, 3H), 3.94 (s, 3H), 7.20-7.39 (m, 3H), 7.70-7.88 (m, 3H) [0061] 13C-NMR (75 MHz, CDCl3 (delta (ppm)); 19.4, 19.8, 52.5, 52.6, 124.4, 126.9, 128.2, 128.9, 129.2, 129.6, 130.2, 133.0, 136.4, 137.1, 137.2, 144.3, 167.5, 168.4 [0062] IR (KBr, cm-1); 3448, 3073, 3030, 2984, 2946, 2914, 2860, 1739, 1714 [0063] Elemental analysis: 72.36% carbon; 5.97% hydrogen [0064] (Theoretical value (C18H18O4): 72.47% carbon; 6.08% hydrogen)

Reference： [1]Patent: US2013/197261,2013,A1 .Location in patent: Paragraph 0055-0064; 0065-0073

37
[ 55499-43-9 ]
[ 95-65-8 ]

Reference： [1]Synlett,2013,vol. 24,p. 1712 - 1714
[2]New Journal of Chemistry,2019,vol. 43,p. 17974 - 17979

38
[ 583-55-1 ]
[ 55499-43-9 ]
[ 89346-62-3 ]

Yield	Reaction Conditions	Operation in experiment
	With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In 1,2-dimethoxyethane; water; at 80℃; for 6h;	3,4-Dimethylbenzeneboronic acid (1d, 12 mmol, 1.2 equiv)And potassium carbonate (15 mmol, 1.5 equiv)And diphenylphosphine palladium dichloride (0.2 mmol, 0.02 equiv) were placed in a 100 mL round bottom flask,While adding 30mLDME (ethylene glycol dimethyl ether)And 6mL H2O,Next, o-bromoiodobenzene (10 mmol, 1.0 equiv)Heated to 80 C for 6 hours.After the reaction,Cool to room temperature,50mL water was added to quench the reaction,Extracted three times with 100 mL of ethyl acetate,The organic phase is dried over anhydrous sodium sulphate,The filtrate was purified by spin column chromatography (eluent: PE) to afford compound 2d.

Reference： [1]Organic Letters,2013,vol. 15,p. 6186 - 6189
[2]Chemical Communications,2014,vol. 50,p. 2193 - 2195
[3]Patent: CN107266411,2017,A .Location in patent: Paragraph 0046; 0047; 0048

39
[ 1663-39-4 ]
[ 55499-43-9 ]
[ 1520075-39-1 ]

Reference： [1]Synthesis,2013,vol. 45,p. 2971 - 2976

40
[ 55499-43-9 ]
[ 65-85-0 ]
[ 3845-63-4 ]

Yield	Reaction Conditions	Operation in experiment
66%	With [bis(acetoxy)iodo]benzene; triethylamine; 1,1'-carbonyldiimidazole; In dichloromethane; at 20℃; for 3h;	General procedure: To a mixture of benzoic acid (1 mmol), carbonyldiimidazole (1mmol), triethylamine, (5 mmol) and boronic acid (1 mmol) in dichlorormethane (5mL) were charged to PhI(OAc)2 (0.38g, 1.2 mmol). The reaction mixture was stirred at room temperature for 3h. After complete conversion, as indicated by TLC (9:1 Hexane:EtOAc), the reaction mixture was evaporated under reduced pressure and theresidue was purified by flash column chromatography on silica gel (2% ethylacetate inpetroleum ether) to give the product.

Reference： [1]Tetrahedron Letters,2014,vol. 55,p. 2345 - 2347

41
[ 55499-43-9 ]
[ 4920-95-0 ]

Reference： [1]Green Chemistry,2014,vol. 16,p. 2865 - 2875

42
[ 95-64-7 ]
[ 55499-43-9 ]

Yield	Reaction Conditions	Operation in experiment
73%		General procedure: To a solution of arylamine (0.5 mmol, 1.0 equiv) in MeOH(1.0 mL) was added HCl (0.5 mL, 1.5 mmol, 3.0 equiv), followed by H2O (0.5 ml). This mixture was stirred 2 min,and the NaNO2 solution (0.25 mL) was then added. The NaNO2 solution was prepared by dissolving 35 mg ofNaNO2 in H2O (0.25 mL). This mixture was stirred 30 minat 0-5 C, followed by HCl (135 mg, 1.5 mmol, 3.0 equivalents) in MeOH (1.0 mL). This mixture was stirred 60min. H2O (10 mL) was added to reaction mixture, then extracted with CH2Cl2 (50 mL, 3×). The combined organic layer was dried over Na2SO4, followed by evaporation to give the products.

Reference： [1]Synlett,2014,vol. 25,p. 1577 - 1584

43
C₂₆H₃₀BrNO₅ [ No CAS ]
[ 55499-43-9 ]
C₃₄H₃₉NO₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	With dichloro[1,1'-bis(di-t-butylphosphino)ferrocene]palladium(II); potassium carbonate; In N,N-dimethyl acetamide; water; at 110℃; for 1h;	Third Step Synthesis of Compound (124) [1229] Compound (123) (14.0 mg, 0.027 mmol) was dissolved in DMA (0.28 mL), and 3,4-dimethylphenylboronic acid (6.10 mg, 0.041 mmol), [1,1?-bis(di-tert-butylphosphino)ferrocene]palladium dichloride (3.53 mg, 0.005 mmol), and a 2 mol/L aqueous potassium carbonate solution (0.027 mL, 0.054 mmol) were added, and the mixture was sealed and stirred at 110 C. for 1 hour. 1 mol/L hydrochloric acid (30 mL) was added, and the mixture was extracted with ethyl acetate (30 mL). The organic layer was washed with 1 mol/L hydrochloric acid (30 mL) and saturated saline (30 mL), and then dried over anhydrous magnesium sulfate. The mixture was concentrated, and then purified by silica gel chromatography (hexane-ethyl acetate), thereby obtaining compound (124) (9.4 mg, 64% yield) as a brown foam substance. [1230] MS: m/z=542.3 [M+H]+

Reference： [1]Patent: US2014/249306,2014,A1 .Location in patent: Paragraph 1224; 1229-1230

44
C₁₀H₁₀Br₂O₃ [ No CAS ]
[ 55499-43-9 ]
C₂₆H₂₈O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
2.61 g	With dichloro[1,1'-bis(di-t-butylphosphino)ferrocene]palladium(II); potassium carbonate; In N,N-dimethyl acetamide; water; at 110℃; for 2h;	Eighth and Ninth Steps Synthesis of Compound (134) [1248] Compound (132) (1.48 g, 8.24 mmol) was dissolved in DMF (30 mL). NBS (3.08 g, 17.3 mmol) was added under ice cooling, and the mixture was stirred for 24 hours while heating to room temperature. Water (50 mL) was added, and the mixture was extracted with ethyl acetate (300 mL). The organic layer was washed with 1 mol/L hydrochloric acid (50 mL×2 times) and saturated saline (50 mL), and then dried over anhydrous magnesium sulfate. The mixture was concentrated, and then the crude product (2.87 g) of the resulting compound (133) was dissolved in DMA (30 mL), and 3,4-dimethylphenylboronic acid (3.18 g, 21.2 mmol), [1,1?-bis(di-tert-butylphosphino)ferrocene]palladium dichloride (553 mg, 0.849 mmol) and a 2 mol/L aqueous potassium carbonate solution (12.7 mL, 25.5 mmol) were added, and then the mixture was sealed and stirred at 110 C. for 2 hours. Water (150 mL) was added, and the mixture was extracted with ethyl acetate (150 mL). An insoluble matter was filtered using celite, and the organic layer was washed with 1 mol/L hydrochloric acid (75 mL×2 times) and saturated saline (50 mL), and then dried over anhydrous magnesium sulfate. The mixture was concentrated, and then purified by silica gel chromatography (hexane-ethyl acetate) to give compound (134) (2.61 g, 82% yield). [1249] MS: m/z=371.2 [M-OH]+

Reference： [1]Patent: US2014/249306,2014,A1 .Location in patent: Paragraph 1233; 1248-1249

45
C₉H₇Cl₂NO₄ [ No CAS ]
[ 55499-43-9 ]
C₂₅H₂₅NO₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 100℃; for 22h;Inert atmosphere;	Fourth Step Synthesis of Compound (5) [0965] Compound (4) (18.5 g, 70.1 mmol) and 3,4-dimethylphenylboronic acid (22.07 g, 147 mmol) were dissolved in dioxane (315 mL), and a 2 mol/L aqueous potassium carbonate solution (105 mL, 210 mmol) was added, and then the operation of degassing and nitrogen substitution was repeated three times. Pd(PPh3)4 (810 mg, 0.701 mmol) was added, and the operation of degassing and nitrogen substitution was again repeated three times, and then the mixture was stirred at 100 C. for 22 hours. The reaction solution was poured into ice water (450 mL) and a 2 mol/L aqueous hydrochloric acid solution (150 mL), and extracted with ethyl acetate. The organic layer was sequentially washed with a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium chloride solution, and dried over anhydrous sodium sulfate, and then the solvent was evaporated under reduced pressure using an evaporator. The resulting residue was purified by silica gel chromatography (hexane-ethyl acetate) to give compound (5) as yellow foam (20.06 g, 71.0% yield). [0966] 1H NMR (CDCl3) delta: 1.85 (s, 3H), 2.27 (s, 3H), 2.29 (s, 3H), 2.30 (s, 3H), 2.31 (s, 3H), 3.64 (s, 3H), 6.80-6.98 (m, 4H), 7.15-7.21 (m, 2H), 8.08 (s, 1H).

Reference： [1]Patent: US2014/249306,2014,A1 .Location in patent: Paragraph 0964-0966

46
[ 55499-43-9 ]
[ 611-73-4 ]
[ 2571-39-3 ]

Reference： [1]RSC Advances,2014,vol. 4,p. 48698 - 48702

47
[ 55499-43-9 ]
[ 24386-93-4 ]
4-amino-5-(3,4-dimethylphenyl)-7-(β-D-ribofuranosyl)-7H-pyrrolo[2,3-d]pyrimidine [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2014,vol. 57,p. 8268 - 8279

48
[ 524-38-9 ]
[ 55499-43-9 ]
C₁₆H₁₃NO₃ [ No CAS ]

Reference： [1]Chemical Communications,2014,vol. 50,p. 12135 - 12138
[2]Angewandte Chemie - International Edition,2016,vol. 55,p. 15166 - 15170
Angew. Chem.,2016,vol. 128,p. 15391 - 15395,5
[3]Journal of the American Chemical Society,2018,vol. 140,p. 42 - 45
[4]Organic Letters,2018,vol. 20,p. 7131 - 7136

49
[ 1252464-84-8 ]
[ 55499-43-9 ]
5-(3,4-dimethylphenyl)-N-methyl-N-(3-methylphenyl)thiophene-2-carboxamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
34%	With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In 1,2-dimethoxyethane; ethanol; water; at 150℃; for 0.333333h;Sealed tube; Inert atmosphere; Microwave irradiation;	General procedure: In a sealed tube the previously prepared bromo-N-heteroarylcarboxamide derivative (1 eq.) was introduced followed by the corresponding boronic acid (1.5 eq.), cesium carbonate (3 eq.), tetrakis(triphenylphosphine)palladium (0.02 eq.) and a mixture of DME/EtOH/H2O (1:1:1, v:v:v, 3 mL) as solvent. The reactor was flushed with N2 and submitted to microwave irradiation (150C, 150 W) for 20 minutes. After cooling to room temperature, a mixture of EtOAc/H2O (1:1, v:v, 2 mL) was added to stop the reaction. The aqueous layer was extracted with EtOAc (3 × 10 mL). The organic layer was washed once with brine and once with water, dried over MgSO4, filtered and the solution was concentrated under reduced pressure. The residue was purified by column chromatography using n-hexane and EtOAc as eluent to afford the desired compound.

Reference： [1]European Journal of Medicinal Chemistry,2014,vol. 87,p. 203 - 219

50
C₁₃H₁₂BrNO₂ [ No CAS ]
[ 55499-43-9 ]
5-(3,4-dimethylphenyl)-N-methyl-N-(m-tolyl)furan-2-carboxamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In 1,2-dimethoxyethane; ethanol; water; at 150℃; for 0.333333h;Sealed tube; Inert atmosphere; Microwave irradiation;	General procedure: In a sealed tube the previously prepared bromo-N-heteroarylcarboxamide derivative (1 eq.) was introduced followed by the corresponding boronic acid (1.5 eq.), cesium carbonate (3 eq.), tetrakis(triphenylphosphine)palladium (0.02 eq.) and a mixture of DME/EtOH/H2O (1:1:1, v:v:v, 3 mL) as solvent. The reactor was flushed with N2 and submitted to microwave irradiation (150C, 150 W) for 20 minutes. After cooling to room temperature, a mixture of EtOAc/H2O (1:1, v:v, 2 mL) was added to stop the reaction. The aqueous layer was extracted with EtOAc (3 × 10 mL). The organic layer was washed once with brine and once with water, dried over MgSO4, filtered and the solution was concentrated under reduced pressure. The residue was purified by column chromatography using n-hexane and EtOAc as eluent to afford the desired compound.

Reference： [1]European Journal of Medicinal Chemistry,2014,vol. 87,p. 203 - 219

51
2-benzyl 3-ethyl (3S)-8-(2-amino-6-((1R)-1-(5-chloro-3'-(methylsulfonyl)[1,1'-biphenyl]-2-yl)-2,2,2-trifluoroethoxy)pyrimidin-4-yl)-2,8-diazaspiro[4.5]decane-2,3-dicarboxylate [ No CAS ]
[ 55499-43-9 ]
2-benzyl 3-ethyl (3S)-8-(2-amino-6-((1R)-1-(3,4-dimethyl-3"-(methylsulfonyl)-[1,1':3',1"-terphenyl]-4'-yl)-2,2,2-trifluoroethoxy)pyrimidin-4-yl)-2,8-diazaspiro[4.5]decane-2,3-dicarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With trans-bis(tricyclohexylphosphine)palladium(II) dichloride; potassium hydrogencarbonate; In 1,4-dioxane; at 100℃;	To a solution of (S)-2-benzyl 3-ethyl 8-(2-amino-6-((R)-l-(5-chloiO-3'-(methylsulfonyl)- [l, -biphenyl]-2-yl)-2J2,2-trifluoroethoxy)pyrimidin-4-yl)-2}8-diazaspiro[4.5]decane-2,3- dicarboxylate (product of Step 1 , Example 34w) (273 mg, 0.34 mmol) in 1,4-dioxane (5 mL) was added <strong>[55499-43-9](3,4-dimethylphenyl)boronic acid</strong> (77 mg, 0.51 mmol), KHCO3 (341 mg, 3.40 mmol), and Pd(PCy3)2 (34 mg, 0,051 mmol). The reaction was heated to 100 C for 44 h. The reaction was charged with additional Pd(PCy3)2 (68 mg, 0.10 mmol) at t = 16 and 39 h. Then the reaction was cooled to RT and extracted with EtOAc, The combined organic layers were dried over N 2S0 ) filtered, and concentrated in vacuo. Purification on a 12 g Isco RediSep silica cartridge (EtOAc/heptane) provided (S)-2-benzyl 3-ethyl 8-(2-amino-6-((R)-l-(3,4-dimethyl-3"- (methylsulfonylMU'^ 'MerphenylM'-yl)^^,^^ diazaspiiO[4.5]decane-2,3-dicarboxylate as an white solid.

Reference： [1]Patent: WO2015/35113,2015,A1 .Location in patent: Page/Page column 222; 223

52
(S)-2-benzyl 3-ethyl 8-(2-amino-6-((R)-1-(4-bromo-2-(3-methyl-1H-pyrazol-1-yl)phenyl)-2,2,2-trifluoroethoxy)pyrimidin-4-yl)-2,8-diazaspiro[4.5]decane-2,3-dicarboxylate [ No CAS ]
[ 55499-43-9 ]
(S)-2-benzyl 3-ethyl 8-(2-amino-6-((R)-1-(3',4'-dimethyl-3-(3-methyl-1H-pyrazol-1-yl)-[1,1'-biphenyl]-4-yl)-2,2,2-trifluoroethoxy)pyrimidin-4-yl)-2,8-diazaspiro[4.5]decane-2,3-dicarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate; In ethanol; water; at 60℃; for 16h;	To a solution of (S)-2-benzyl 3-ethyl 8-(2-amino-6-((R)-l -(4-bromo-2-(3-metliyl-lH- pyrazol-l -yl)phenyl)-2,2,2-trifiuoi ethoxy)pyrimidin-4-yl)-2J8-diazaspii [4.5]decane-2,3- dicarboxylate (Step 2, Example lu) (300 mg, 0.4 mmol, Step 2) in ethanol (2 mL) and water (0.5 mL) was added <strong>[55499-43-9](3,4-dimethylphenyl)boronic acid</strong> (120 mg, 0.8 mmol), PdCl2(PPh3)2 (41 mg, 0.058 mmol), and Cs2C03 (390 mg, 1.2 mmol). The reaction was heated to 60 C for 16 h, then cooled to RT, filtered through celite and concentrated in vacuo. Purification by normal phase silica gel column (EtO Ac/heptane) provided (S)-2-benzyl 3-ethyl 8-(2-amino-6-((R)-l-(3'J4'- dimethyl-3-(3-methyl-lH-pyrazol-l-yl)-[l,l,-biphenyl]-4-yl)-2,2)2 rifluoroethoxy)pyrimidin-4- yl)-2,8-diazaspiro[4.5]decane-2>3-dicarboxylate as a white solid

Reference： [1]Patent: WO2015/35113,2015,A1 .Location in patent: Page/Page column 89

53
4-bromo-N-(3-methoxyphenyl)-N-methylbenzamide [ No CAS ]
[ 55499-43-9 ]
N-(3-methoxyphenyl)-N,3',4'-trimethyl-[1,1'-biphenyl]-4-carboxamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In 1,2-dimethoxyethane; ethanol; water; at 150℃; for 0.333333h;Sealed tube; Inert atmosphere; Microwave irradiation;	General procedure: In a sealed tube the previously prepared bromo-N-heteroarylcarboxamide derivative (1 eq.) was introduced, followed by the corresponding boronic acid (1.5 eq.), cesium carbonate (3 eq.), tetrakis(triphenylphosphine)palladium (0.02 eq.) and a mixture of DME/EtOH/H2O (1:1:1, v:v:v, 3 mL) as solvent. The reactor was flushed with N2 and submitted to microwave irradiation (150 C, 150 W) for 20 minutes. After cooling to room temperature, a mixture of EtOAc/H2O (1:1, v:v, 2 mL) was added to stop the reaction. The aqueous layer was extracted with EtOAc (3 × 10 mL). The organic layer was washed once with brine and once with water, dried over MgSO4, filtered and the solution was concentrated under reduced pressure. The residue was purified by column chromatography using hexanes and EtOAc as eluent to afford the desired compound.

Reference： [1]PLoS ONE,2015,vol. 10

54
pyridin-2-yl 2,3,4,5,6-pentafluorobenzenesulfonate [ No CAS ]
[ 55499-43-9 ]
[ 4423-81-8 ]

Yield	Reaction Conditions	Operation in experiment
86%	With bis-triphenylphosphine-palladium(II) chloride; potassium phosphate monohydrate; In tert-butyl alcohol; at 28℃; for 12h;Schlenk technique; Inert atmosphere; Sealed tube;	General procedure: Procedure A: To a Schlenk tube equipped with a magnetic stiring bar and a teflon septum was charged K3PO4.H2O (1.5 mmol, 3 equiv), aryl pentafluorobenzene sulfonate (0.5 mmol, 1.0 equiv), aryl boronic acid (0.75 mmol, 1.5 equiv) and Pd(PPh3)2Cl2 (0.015 mmol, 3 mol%). The tube was then capped with a rubber septum, evacuated and backfilled with nitrogen and this cycle was repeated twice. Under an inertatmosphere, tert - butanol (3 mL) was added via syringe. Under a positive pressure of nitrogen, the rubber septum was replaced with a Teflon screw cap and this was sealed. The Schlenk tube was stirred at room temperature for the time indicated. When the reaction was completed according to TLC or GCMS (FID), thereaction mixture was diluted with EtOAc (5 mL) and filtered through celite bed. The organic layer was concentrated under reduced pressure. The residue was purified through silica gel (230 - 400 mesh) column chromatography using 1-10% ethyl acetate in petroleum ether to afford the product.

Reference： [1]Tetrahedron Letters,2015,vol. 56,p. 5106 - 5111

55
[ 3638-04-8 ]
[ 55499-43-9 ]
2-chloro-4-(3,4-dimethylphenyl)-6-methoxy-1,3,5-triazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In toluene; at 100℃; for 2h;Inert atmosphere;	Under an argon atmosphere, to a suspension of 3,4-dimethylbenzeneboronic acid (0.42 g, 2.8 mmol), <strong>[3638-04-8]2,4-dichloro-6-methoxy-1,3,5-triazine</strong> (1.0 g, 5.6 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.32 g, 0.28 mmol) in toluene (8.4 ml) was added 2M aqueous sodium carbonate solution (4.2 ml), and the mixture was stirred at 100 C. for 2 hr. At room temperature, to the reaction mixture were added water and ethyl acetate, and the mixture was partitioned. The organic layer was washed with saturated brine, dried over sodium sulfate, filtered to remove sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate=20/1) to give the title compound (0.64 g, 92%). (0907) 1H-NMR (CDCl3) delta: 2.35 (6H, s), 4.16 (3H, s), 7.26 (3H, d, J=7.8 Hz), 8.22 (1H, dd, J=7.8, 2.1 Hz), 8.25 (1H, d, J=2.1 Hz).

Reference： [1]Patent: US2015/266834,2015,A1 .Location in patent: Paragraph 0905-907

56
4-oxo-3-[4-(trifluoromethylsulfonyloxy)phenyl]-4Hchromen-7-yl trifluoromethanesulfonate [ No CAS ]
[ 55499-43-9 ]
C₃₀H₂₁F₃O₅S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 85℃; for 6h;Inert atmosphere;	General procedure: The reactions were carried out in a pressure tube. A solution of2 (70 mg, 0.135 mmol ), K2CO3 (2 mL, 2 M,), Pd(PPh3)4 (3 mol%)and arylboronic acid 3 (1.2 equiv) in DMF (4 mL) was stirred at85 C for 6 h under an Ar atm. To the mixture were added H2O(20 mL) and CH2Cl2 (25 mL). The organic and aq layers were separatedand the latter was extracted with CH2Cl2 (2 × 20 mL). Thecombined organic layers were dried (Na2SO4), filtered and thefiltrate was concentrated in vacuo. The residue was purified bycolumn chromatography (silica gel, heptane-EtOAc, 9:1).

Reference： [1]Synlett,2015,vol. 26,p. 2527 - 2530

57
[ 14002-33-6 ]
[ 55499-43-9 ]
10-(3,4-dimethylphenyl)octahydro-[1,3,2]oxazaborinino[2,3-b][1,3,2]oxazaborinin-5-ium-10-uide [ No CAS ]

Reference： [1]Dalton Transactions,2015,vol. 44,p. 20577 - 20583

58
C₁₀H₁₀Br₂O₂ [ No CAS ]
[ 55499-43-9 ]
C₁₈H₁₉BrO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With tetrakis(triphenylphosphine) palladium(0); thallium(I) nitrate; potassium carbonate; In tetrahydrofuran; water; at 35℃; for 24h;Inert atmosphere;	General procedure: To a flame-dried 10-mL round-bottom flask was added IV(1.0 mmol, 1.0 equiv),thallium nitrate(3.6 mmol, 3.6 equiv), potassium carbonate(1.8 mmol, 1.8equiv)boric acid(1.1 mmol, 1.1 equiv), Tetrakis(triphenylphosphine)palladium (0.1mmol, 0.1 equiv) and solvent( THF:H2O = 4ml:2ml), bubbled with Ar ball for half hour. Stirring was continued for 24 h at 35.The mixture was extracted withethyl acetate three times and the combined organic phase was washed withsaturated brine, dried (Na2SO4), filtered, and concentrated under reduced pressure.The residue was purified by silica gel column chromatography to afford V(EtOAc :Hexane = 1:8).

Reference： [1]Synlett,2016,vol. 27,p. 1602 - 1606

59
[ 201230-82-2 ]
[ 640-60-8 ]
[ 55499-43-9 ]
[ 2571-39-3 ]

Reference： [1]RSC Advances,2016,vol. 6,p. 86502 - 86509

60
[ 201230-82-2 ]
[ 17763-67-6 ]
[ 55499-43-9 ]
[ 2571-39-3 ]

Reference： [1]RSC Advances,2016,vol. 6,p. 86502 - 86509

61
[ 55499-43-9 ]
1,1-dimethyl-2-iodo-inden-3-yl-dicyclohexylphosphino [ No CAS ]
C₃₁H₄₁P [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
38%	With potassium phosphate tribasic trihydrate; palladium diacetate; In tetrahydrofuran; at 110℃; for 24h;Inert atmosphere;	Under the nitrogen atmosphere, to the high-pressure reaction in1,1-dimethyl-2-iodo-3-indenyl dicyclohexyl phosphino (0.140 g, 3 . 00×10-4mol) was added 3,4-methylphenyl boronic acid (0.0640 g, 3 . 60×10-4mol), tri hydrated potassium phosphate (0.240 g, 9 . 00×10-4mol), palladium acetate (6.90×10-4grams, 3.00×10-6mol) as catalyst, by adding tetrahydrofuran (1.20 ml) as a solvent, in 110 C lower, reaction 24 hours, the reaction is stopped, vacuum to remove thf, the resulting solid chromatographic column for separation, to obtain 0.0507 g compound 18, yield 38%.

Reference： [1]Patent: CN105330692,2016,A .Location in patent: Paragraph 0011 ; 0088 ; 0090

62
[ 55499-43-9 ]
3-bromo-4-methyl-2-oxo-2H-chromene-6,7-diyl bis(trifluoromethanesulfonate) [ No CAS ]
3,6,7-tris(3,4-dimethylphenyl)-4-methyl-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 120℃; for 10h;Inert atmosphere;	General procedure: The reactions were carried out in a pressure tube. A 1,4-dioxane solution (4 mL) of 11 (70 mg, 0.13 mmol), arylboronic acid (3.1 equiv, 0.41 mmol), aqueous K2CO3 (2 M, 2 mL), and Pd(PPh3)4 (14 mg, 9 mol%, 0.012 mmol) was heated at 120 C for 10 h under argon atmosphere. After cooling to 20 C, water was added and the reaction mixture was extracted with CH2Cl2 (3 × 25 mL). The organic layers were dried (Na2SO4), filtered and concentrated in vacuo. The residue was purified by column chromatography (silica gel, heptane/EtOAc=9:1).

Reference： [1]Bioorganic and Medicinal Chemistry,2016,vol. 24,p. 5115 - 5126

63
[ 55499-43-9 ]
2-bromo-7-methyl-5-oxo-5H-1,3,4-thiadiazolo<3,2-a>pyrimidine [ No CAS ]
7-methyl-2-(3,4-dimethylphenyl)-5H-1,3,4-thiadiazolo[3,2-a]-pyrimidin-5-one [ No CAS ]

Reference： [1]RSC Advances,2016,vol. 6,p. 107556 - 107571

64
[ 1352052-18-6 ]
[ 55499-43-9 ]
6-fluoro-7-methyl-2-(3,4-dimethylphenyl)-5H-1,3,4-thiadiazolo[3,2-a]pyrimidin-5-one [ No CAS ]

Reference： [1]RSC Advances,2016,vol. 6,p. 107556 - 107571

65
[ 55499-43-9 ]
10-bromo-8-cyclopropyl-7,8-dihydropyrido[2′,3′:4,5]pyrrolo[1,2-a]pyrazin-9(6H)-one [ No CAS ]
8-cyclopropyl-10-(3,4-dimethylphenyl)-7,8-dihydropyrido[2’,3’:4,5]pyrrolo[1,2-a]pyrazin-9(6H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate; In 1,4-dioxane; at 70℃; for 20h;Inert atmosphere;	A suspension of C9 (61 mg, 0.20 mmol) in degassed 1 4-dioxane (0.8 mL) was added to the appropriate substituted phenylboronic acid (0.3 mmol) in a vial.Aqueous potassium carbonate solution (3M, 0.2 mL, 0.6 mmol) and [1,1?- bis(diphenylphosphino)ferrocene]dichloropalladium(II), dichloromethane complex (8 mg, 0.01 mmol) were introduced, and the reaction mixture was degassed via two cycles of vacuum evacuation followed by nitrogen fill. The reaction mixture was heated with shaking at 70 C for 20 hours, then partitioned between water (1.5 mL) and ethyl acetate (2.5 mL). The organic layer was loaded onto an SCX-2 solid phase extraction cartridge (Silicycle, 6 mL, 1 g). Extraction of the aqueous layer was carried out twice more, and the organic layers were loaded onto the same cartridge. The cartridge was eluted with methanol (5 mL), and then with a solution of triethylaminein methanol (1 M, 7.2 mL); the basic eluent was collected and concentrated in vacuo. Products were purified via reversed phase HPLC (Column: Waters XBridge Cl 8, 5 pm; Mobile phase A: 0.03% ammonium hydroxide in water (vlv); Mobile phase B:0.03% ammonium hydroxide in acetonitrile (vlv); Gradient: 10% to 100% B).

Reference： [1]Patent: WO2016/203347,2016,A1 .Location in patent: Page/Page column 152; 153; 159

66
[ 55499-43-9 ]
[ 34082-45-6 ]
(S)-2-(3,4-dimethylphenyl)-2-phenylbenzofuran-3(2H)-one [ No CAS ]

Reference： [1]Organic Letters,2017,vol. 19,p. 2726 - 2729

67
[ 55499-43-9 ]
3-bromo-5-nitro-2(1H)-pyridinone [ No CAS ]
3-(3,4-dimethylphenyl)-5-nitropyridin-2(1H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
54%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 100℃; for 10h;Inert atmosphere;	General procedure: To the mixture solution of 3-bromo-5-nitropyridin-2(1H)-one (5) (2g, 9.13mmol) and different substituted benzeneboronic acid (1.53g, 10.05mmol) in water (15mL)and 1,4-dioxane (45mL)were added with K2CO3 (3.79g, 27.4mmol). The reaction mixture was added Pd(PPh3)4 under N2 atmosphere and stirred at 100C for 10h under reflux. Upon completion of the reaction, the solvent was evaporated, leaving a residue which was treated with water (60mL) and extracted with ethyl acetate (3×25mL). The organic layer was washed with salt solution (50mL x 3), dried over anhydrous sodium sulfate, and then the solvent was removed under vacuum. The residue was washed with methanol again and dried, giving the desired compounds (6a-6h) in good yield [25].

Reference： [1]European Journal of Medicinal Chemistry,2017,vol. 136,p. 144 - 153

68
[ 55499-43-9 ]
C₁₅H₁₆BrNO₃ [ No CAS ]
(5-methylfuran-2-yl)methyl (2-(3',4'-dimethyl-[1,1'-biphenyl]-4-yl)ethyl)carbamate [ No CAS ]

Reference： [1]Organic Letters,2017,vol. 19,p. 2833 - 2836

69
[ 55499-43-9 ]
4-chloro-5-methyl-2-phenylpyridine [ No CAS ]
4-(3,4-dimethylphenyl)-5-methyl-2-phenylpyridine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); potassium phosphate monohydrate; In 1,2-dimethoxyethane; water; at 100℃; for 16h;Inert atmosphere;	4-Chloro-5-methyl-2-phenylpyridine (6 g, 29.5 mmol), <strong>[55499-43-9](3,4-dimethylphenyl)boronic acid</strong> (4.86 g, 32.4 mmol), and potassium phosphate tribasic hydrate (13.57 g, 58.9 mmol) were dissolved in a mixture of DME (60 ml)/water (2 mL) under nitrogen to give a colorless suspension. Pd2(dba)3 (0.405 g, 0.442 mmol) and SPhos (0.410 g, 0.884 mmol) were added as one portion, before the reaction mixture was degassed and heated to 100 C. under nitrogen for 16 h. The reaction mixture was then cooled down to room temperature (22 C.). The organic phase was separated, evaporated, and purified by column chromatography using a silica gel column eluted with heptanes/THF 95/5 (v/v), then crystallized from heptanes to yield white crystals (7.0 g, 85% yield).

Reference： [1]Patent: US2017/294597,2017,A1 .Location in patent: Paragraph 0137; 0138; 0139

70
[ 55499-43-9 ]
2-bromo-7-trifluoromethyl-5H-[1,3,4]thiadiazolo[3,2-a]pyrimidin-5-one [ No CAS ]
2-(3,4-di-methylphenyl)-7-trifluoromethyl-5H-1,3,4-thiadiazolo[3,2-a]pyrimidin-5-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
63%	With palladium diacetate; potassium carbonate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In 1,4-dioxane; at 100℃; for 16h;	General procedure: A mixture of 2-bromo-7-trifluoromethyl-5H-1,3,4-thiadiazolo[3,2-a]pyrimidin-5-one (1.0 equiv., 0.335mmol), arylboronic acid (1.1 equiv.), Palladium(II)acetate (0.1 equiv.), Xantphos (0.2 equiv.) and Potassium carbonate (2.0 equiv.) was vigorously stirred and heated in dry 1,4-dioxane (2ml) at 100C for 16h. After cooling to room temperature, the reaction mixture was diluted with water and extracted into ethyl acetate. The organic layer was dried with anhydrous sodium sulfate and the solvent was evaporated. The crude compound was purified by flash column chromatography on silicagel (ethyl acetate:heptane).

Reference： [1]European Journal of Medicinal Chemistry,2018,vol. 144,p. 116 - 127
[2]Medicinal Chemistry,2020,vol. 16,p. 689 - 702

71
[ 104-92-7 ]
[ 55499-43-9 ]
4'-methoxy-3,4-dimethyl-1,1'-biphenyl [ No CAS ]

Reference： [1]Applied Organometallic Chemistry,2019,vol. 33
[2]New Journal of Chemistry,2018,vol. 42,p. 2364 - 2367

72
[ 3460-18-2 ]
[ 55499-43-9 ]
4-bromo-3',4'-dimethyl-2-nitro-1,1'-biphenyl [ No CAS ]
3,3'',4,4''-tetramethyl-2'-nitro-1,1': 4',1''-terphenyl [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
54%; 24%	With palladium diacetate; potassium carbonate; In tetrahydrofuran; water; at 0℃; for 2h;	General procedure: To an oven dried round bottomed flask fitted with a stirring barand rubber septum was added 1,4-dibromo-2-nitrobenzene (1) (70 mg, 0.25 mmol), the boronic acid (0.25 mmol), Pd(OAc)2 (4 mg, 7 mol%) and K2CO3 (69 mg, 0.5 mmol). A mixture of THF/H2O (1/1) (2 mL) at 0 C was added by syringe and the resulting mixture stirred for 2 h at 0 C (some reactions were carried out at 25 C for 2 h or 24 h). the reaction was quenching with water (50 mL), followed by neutralizing with HCl when necessary. The mixture was extracted with CH2Cl2, washed with brine, dried over MgSO4, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel. The conversion and product ratios were calculated from the 1H NMR spectra of the crude products, using the integration of the proton para to the nitro group at ca 7.9 ppm (alternatively, integration of the proton adjacent to the nitro group at ca 7.7 ppm could be used).

Reference： [1]Tetrahedron,2018,vol. 74,p. 1731 - 1741

73
[ 3460-18-2 ]
[ 5720-07-0 ]
[ 55499-43-9 ]
4-methoxy-3",4"-dimethyl-2'-nitro-1,1':4',1''-terphenyl [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%		To an oven dried round bottomed flask with a stir bar and rubber septum was added 1,4-dibromo-2-nitrobenzene (1) (70 mg, 0.25 mmol), 4-methoxyphenylboronic acid (2) (38 mg, 0.25 mmol), Pd(OAc)2 (4 mg, 7 mol%) and K2CO3 (69 mg, 0.5 mmol). A mixture of THF/H2O (1/1) (2 mL) at 0 C was added by syringe and the resulting mixture was stirred for 4 h at 0 C. The second boronic acid (0.25 mmol) was then added and the resulting mixture was stirred at 25 C for 16 h before quenching the reaction with water (50 mL) and extraction with CH2Cl2. The CH2Cl2 extract was washed with brine, dried over MgSO4, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel. The conversion and product ratios were calculated from the 1H NMR spectra of the crude products, using the integration of the proton para to the nitro group at ca 7.9 ppm (alternatively, integration ofthe proton adjacent to the nitro group at ca 7.7 ppm could be used). 3.3.1. 4-Methoxy-3",4"-dimethyl-2'-nitro-1,1':4',1"-terphenyl (23). Following the general method 2, with 3,5-dimethylphenylboronic acid (38 ?mg, 0.25? mmol) as the second boronic acid, flash column chromatography of the crude product on silica gel (n-hexane/EtOAc, 5:1) gave 4-methoxy-3",4"-dimethyl-2'-nitro-1,1':4',1"-terphenyl (23) as a yellow solid (74?mg, 89% yield); m. p. 92.4?C; 1H NMR (CDCl3) delta 2.33 (s, 3H), 2.35 (s, 3H), 3.85 (s, 3H), 6.96 (d, 2H, J?=?8.8?Hz), 7.24 (br. d, 1H, J?=?7.8?Hz), 7.28 (d, 2H, J?=?8.8?Hz), 7.36 (br. dd, 1H, J?=?7.8, 1.9?Hz), 7.41 (br. s, 1H), 7.45 (d, 1H, J?=?8.0?Hz), 7.78 (dd, 1H, J?=?8.0, 1.9?Hz), 7.99 (d, 1H, J?=?1.9?Hz); 13C NMR (CDCl3) delta 19.7, 20.1, 55.5, 114.5 (2x), 122.4, 124.5, 128.4, 129.4 (2x), 129.5, 130.4, 130.6, 132.4, 134.2, 136.1, 137.4, 137.7, 141.4, 149.9, 159.9; HRMS(ESI): m/z [M+H]+ calcd for C21H20NO3: 334.1443, found 334.1444.

Reference： [1]Tetrahedron,2018,vol. 74,p. 1731 - 1741

74
[ 132153-48-1 ]
[ 55499-43-9 ]
2-NH-Boc-3-(3’4’–dimethyl-[1,1’-biphenyl]-4)propionic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; In 1,4-dioxane; water; at 25 - 100℃; for 5h;Inert atmosphere;	3-(4-bromophenyl)-2-NH-Boc-propionic acid,(3,4-Diphenyl)boronic acidAnd potassium carbonate dissolves in water and dioxane,Pd(dppf)Cl2 is added at room temperature 25C.Raise the temperature to 100C in a nitrogen atmosphere.Stir for 5 hours,Reaction generation2-NH-Boc-3-(3',4'-dimethyl-[l,l'-biphenyl]-4)propanoic acid

Reference： [1]Patent: CN107903191,2018,A .Location in patent: Paragraph 0006-0007

75
[ 22364-29-0 ]
[ 55499-43-9 ]
[ 56106-09-3 ]

Reference： [1]Angewandte Chemie - International Edition,2018,vol. 57,p. 8848 - 8853
Angew. Chem.,2018,vol. 130,p. 8986 - 8991,6

76
[ 1700-02-3 ]
[ 55499-43-9 ]
[ 50786-91-9 ]

Yield	Reaction Conditions	Operation in experiment
63.5%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 150℃; for 24h;Inert atmosphere;	In a 250ml three-neck bottle,Under the protection of nitrogen,Add 0.05 mol of 2,4-dichloro-6-phenyl-1,3,5-triazine,0.15 mol of 3,4-dimethylphenylboronic acid,150 ml of toluene was mixed and mixed.Then add 0.015 mol Pd(PPh3)4,0.15mol of potassium carbonate is dissolved in a 1:1 mixed solution of water and ethanol.Heat to 150 C, reflux reaction for 24 hours, sample the plate,No raw material remaining, the reaction is complete; naturally cooled to room temperature,Filtration, and the filtrate was subjected to vacuum distillation (-0.09 MPa, 85 C).Over neutral silica gel column,Obtaining 2,4-di-(3,4-dimethylphenyl)-6-phenyl-[1,3,5]triazine,HPLC purity 99.0%, yield 63.5%.

Reference： [1]Patent: CN108148048,2018,A .Location in patent: Paragraph 0102; 0105; 0107

77
[ 108-86-1 ]
[ 55499-43-9 ]
[ 4433-11-8 ]

Yield	Reaction Conditions	Operation in experiment
94%Chromat.	With sodium carbonate; In ethanol; at 80℃; for 4h;Inert atmosphere;	General procedure: In a typical reaction procedure, bromobenzene (0.4 mmol),4-methylbenzeneboronic acid (0.1 mmol), Pd1Ni4/ZrO2 alloy catalyst and Na2CO3 (1 equiv.) were added into a reactor (10 mL) equipped with a magnetic stirrer and EtOH (2 mL) was added as the solvent. The reaction mixture was stirred at 80 C under an N2 atmosphere for 4 h. After reaction, the catalyst was separated by simple filtration and the solution was analysed by GC and GC-MS. For isolation of the products, the solvent was removed under reduced pressure. The residue was purified by flash chromatography on a silica column, using ethylacetate and n-hexane as the eluent. The NMR data for the products agreed with the literature

Reference： [1]Journal of Chemical Research,2018,vol. 42,p. 419 - 423

78
[ 55499-43-9 ]
8-bromo-1,2,3,5,6,7-hexahydro-s-indacen-4-amine [ No CAS ]
1,2,3,5,6,7-hexahydro-8-(3,4-dimethylphenyl)-s-indacen-4-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate; In 1,4-dioxane; water; at 80℃; for 16h;	8-Bromo-l,2,3,5,6,7-hexahydro-s-indacen-4-amine (105 mg, 0.42 mmol), 3,4-dimethylphenyl- boronic acid (187 mg, 1.25 mmol), Pd(dppf)Cl2 (30.4 mg, 0.04 mmol) and dioxane (1.5 mL) were added to a reaction vial. Cesium carbonate (1.24 mL, 1 M in H2O) was then added and the reaction mixture was stirred at 80 C for 16 h. Reaction mixture was brought to RT and filtered through a small bed of Celite and rinsed with dioxane (5 mL). Water (5 mL) was added to the filtrates and extracted with diethyl ether (5 mL x 3). The combined organic layers were washed with brine, dried over anhydrous MgS04, filtered, and concentrated in vacuo to provide titled compound which was used in the next step without any purification. LCMS [M+H]+= 278.4.

Reference： [1]Patent: WO2019/23147,2019,A1 .Location in patent: Page/Page column 639

79
[ 55499-43-9 ]
[ 77802-38-1 ]
N-(2,3-dihydro-4-(3,4-dimethylphenyl)-1H-inden-7-yl)acetamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate; In 1,4-dioxane; water; for 72h;Heating;	A mixture of N-(4-bromo-2,3-dihydro-lH-inden-7-yl)acetamide (1 g, 3.9 mmol), 3,4- dimethylphenylboronic acid (700 mg, 4.68 mmol), Pd(dppf)Cl2.DCM (160 mg, 0.19 mmol), sodium carbonate (900 mg, 8.58 mmol as 2 M aqueous solution) in dioxane (12 mL) was stirred at 100 C in an oil bath for 72 h. The reaction mixture was brought to RT, water (20 mL) was added and extracted with EtOAc (15 mL x 3). The combined organic layers were washed with brine, dried over MgS04, filtered, and concentrated in vacuo. The crude product was purified by silica gel flash chromatography using 0- 30% gradient of EtOAc in hexanes to afford titled compound (880 mg, 81%). LCMS [M+H]+= 280.6.

Reference： [1]Patent: WO2019/23147,2019,A1 .Location in patent: Page/Page column 637; 638

80
[ 32889-11-5 ]
[ 40307-11-7 ]
[ 55499-43-9 ]
(E)-3-(3,4-dimethylphenyl)-4-(4-ethylphenyl)-N-(quinolin-8-yl)but-3-enamide [ No CAS ]

Reference： [1]Organic Letters,2019,vol. 21,p. 6034 - 6039

81
[ 51608-60-7 ]
[ 55499-43-9 ]
C₂₂H₂₃NO₂S [ No CAS ]

Reference： [1]RSC Advances,2019,vol. 9,p. 25377 - 25381

82
[ 53181-22-9 ]
[ 55499-43-9 ]
2-[(4-chlorophenyl)amino]-2-(3,4-dimethylphenyl)-1-phenylethan-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71%	With [2,2]bipyridinyl; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; In methanol; at 80℃;Inert atmosphere;	N- (4-chlorophenyl) -1-phenylethyl ketone, alpha, alpha, alpha-bipyridine, 2,2,6,6-tetramethylpiperidine oxide, 3,4-dimethyl Phenylboronic acid was added to the reaction tube, after adding nitrogen, methanol was added, and the reaction solution was obtained after the reaction was completed at 80 C. The N- (4-chlorophenyl) -1-phenylethyl ketone and 3 The molar ratios of 4,4-dimethylphenylboronic acid, alpha, alpha, alpha-bipyridine, 2,2,6,6-tetramethylpiperidine oxide, and methanol are 1: 1.2, 1: 0.1, 1: 1.2, 1:40; extracting the reaction solution under reduced pressure to remove the organic solvent to obtain an extract solution; the extract solution was dried, filtered, separated and purified by silica gel column chromatography, and concentrated by rotary evaporation to obtain N- (4 -Chlorophenyl) -1-phenyl-2- (3,4-dimethylphenyl) ethanone.

Reference： [1]RSC Advances,2019,vol. 9,p. 32081 - 32084
[2]Patent: CN110668960,2020,A .Location in patent: Paragraph 0036-0037

83
[ 5419-55-6 ]
[ 583-71-1 ]
[ 55499-43-9 ]

Yield	Reaction Conditions	Operation in experiment
		Compound 1 (10 g, 54.05 mmol) and tetrahydrofuran (anhydrous) (100 mL) were added to a 250 mL reaction bottle and mixed by stirring.After compound 1 is completely dissolved,Cool the reaction bottle to -78 C. andN-butyllithium (2.5M, 32.4 mL, 81.08 mmol) was added slowly,Let react for 0.5 hour, add triisopropyl borate (20.3 g, 108.1 mmol) to the reaction bottle at -78 C.,The mixture in the reaction bottle was reacted at 0 C. for 1 hour.After the reaction is completeDilute hydrochloric acid (1N, 80 mL) was added to the reaction bottle,The reaction mixture was obtained by stirring at 20 C. to 30 C. for 0.5 hour.Then extract the reaction mixture with ethyl acetate and water, collect the organic layer,The solvent in the organic layer was removed using a rotary evaporator to obtain a crude product.The crude product is purified by column chromatography,Compound 6 was obtained as a white solid.

Reference： [1]Patent: JP2019/156840,2019,A .Location in patent: Paragraph 0124-0126

84
[ 40396-54-1 ]
[ 55499-43-9 ]
1-(3',4'-dimethyl-[1,1'-biphenyl]-3-yl)-2-phenylethane-1,2-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In 1,4-dioxane; water; at 100℃; for 3h;Inert atmosphere;	General procedure: A dried radius flask was charged with T-1 (115.2 mg, 0.4 mmol, 1.0 equiv.),4-biphenylboronic acid (158.4 mg, 0.8 mmol, 2.0 equiv.), Pd(PPh3)2Cl2(28.08 mg, 0.04 mmol, 10 mol %), K2CO3 (165.6mg, 1.2 mmol, 3 equiv.), H2O (100 muL) and 1,4-dioxane (4.0 mL). Themixture was stirred at 100 C for 3 h under nitrogen. Upon completion of thereaction as monitored by TLC, the reaction was allowed to cool to roomtemperature, and extracted with ethyl acetate (20 mL × 3). The organic phasewas collected and washed with brine, dried over with anhydrous Na2SO4,ltered, and concentrated. The filtrate was evaporated under reduced pressure,and the residue was purified by column chromatography on silica gel usingpetroleum ether/ethyl acetate as eluent to afford the desired product T-2 (136.4 mg, 94 %) as yellow solid.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2019,vol. 29

85
[ 925-18-8 ]
[ 2039-85-2 ]
[ 55499-43-9 ]
4-(5-bromo-1-(3-chlorophenyl)pentyl)-1,2-dimethyl benzene [ No CAS ]

Reference： [1]Organic Letters,2020,vol. 22,p. 620 - 625

86
[ 105-74-8 ]
[ 827-54-3 ]
[ 55499-43-9 ]
2-(1-(3,4-dimethylphenyl)tridecyl)naphthalene [ No CAS ]

Reference： [1]Organic Letters,2020,vol. 22,p. 620 - 625

87
[ 55499-43-9 ]
2,6-anhydro-3,4-O-carbonate-1,5-dideoxy-L-arabino-hex-5-enitol [ No CAS ]
(2S,3S,6R)-6-(3,4-dimethylphenyl)-2-methyl-3,6-dihydro-2H-pyran-3-ol [ No CAS ]

Reference： [1]Organic Letters,2020,vol. 22,p. 1144 - 1148

88
[ 272-24-2 ]
[ 55499-43-9 ]
5-(3,4-dimethylphenyl)thieno[2,3-d]pyrimidine [ No CAS ]

Reference： [1]Organic Letters,2020,vol. 22,p. 1547 - 1551

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P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

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

[ CAS No. 55499-43-9 ] {[proInfo.proName]}

Quality Control of [ 55499-43-9 ]

Related Doc. of [ 55499-43-9 ]

Product Details of [ 55499-43-9 ]

Calculated chemistry of [ 55499-43-9 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 55499-43-9 ]

Application In Synthesis of [ 55499-43-9 ]

[ 55499-43-9 ] Synthesis Path-Upstream 1~9

[ 55499-43-9 ] Synthesis Path-Downstream 1~88

Related Functional Groups of [ 55499-43-9 ]

Organoboron

Aryls

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

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[ 55499-43-9 ]