Name: 4688-76-0|2-Biphenylboronic acid|98%
Brand: Ambeed
SKU: A182624
Price: 5.0 USD
Availability: InStock
Rating: 96 (35 reviews)

1
[ 16932-45-9 ]
[ 4688-76-0 ]
[ 223268-67-5 ]

Reference： [1]Tetrahedron,1999,vol. 55,p. 3455 - 3466
[2]Tetrahedron Letters,1996,vol. 37,p. 3161 - 3164

2
[ 3401-47-6 ]
[ 4688-76-0 ]
[ 186465-05-4 ]

Yield	Reaction Conditions	Operation in experiment
99%	With potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); 1-(7-benzofuranyl)-2-di(3,5-di-tert-butyl-4-methoxyphenyl)phosphinenaphthalene; In toluene; at 80℃; for 0.5h;Glovebox; Inert atmosphere;	In a glove box, 1.0 mmol of 1-bromo-2-methoxynaphthalene, 2.0 mmol of aryl boronic acid, Pd2 (dba) 3, phosphine ligand and 3.0 mmol of potassium phosphate were charged in 7 mL of anhydrous toluene under nitrogen , And the temperature was raised to 80 C, and the reaction was carried out for a period of time. The results are shown in Table 2 below.The amount of Pd2 (dba) 3 and the phosphine ligand is divided into two kinds: (1) 0.25 mol% Pd2 (dba) 3, 0.5 mol% phosphine ligand, or (2) 0.5 mol% Pd2 (dba) mol% phosphine ligand, depending on the amount of ligand used in Table 2.

Reference： [1]Organometallics,2014,vol. 33,p. 2099 - 2108
[2]Patent: CN106995461,2017,A .Location in patent: Paragraph 00142-0144; 0153
[3]New Journal of Chemistry,2018,vol. 42,p. 5967 - 5971
[4]European Journal of Inorganic Chemistry,2017,vol. 2017,p. 4028 - 4048
[5]Organic Letters,2012,vol. 14,p. 4250 - 4253
[6]Tetrahedron Letters,1996,vol. 37,p. 9245 - 9248
[7]European Journal of Organic Chemistry,2014,vol. 2014,p. 6676 - 6685

3
[ 3972-65-4 ]
[ 4688-76-0 ]
2-(4-tert-butylphenyl)biphenyl [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2004,vol. 43,p. 1871 - 1876
[2]Journal of the American Chemical Society,2005,vol. 127,p. 4685 - 4696

4
[ 3975-77-7 ]
[ 4688-76-0 ]
1-phenyl-2-[2-methyl-2-(3,5-di-tert-buthylphenyl)propyl]benzene [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2005,vol. 127,p. 4685 - 4696
[2]Journal of Organic Chemistry,2013,vol. 78,p. 11513 - 11524

5
[ 7051-15-2 ]
[ 4688-76-0 ]
[ 223268-67-5 ]

Reference： [1]Journal of the American Chemical Society,2005,vol. 127,p. 4685 - 4696

6
[ 104-21-2 ]
[ 4688-76-0 ]
2-(4-methoxybenzyl)-1,1'-biphenyl [ No CAS ]

Reference： [1]Chemical Communications,2005,p. 5899 - 5901

7
(S)-2-(tert-butoxycarbonylamino)-5-(3-(2,2,4,6,7-pentamethyl-2,3-dihydrobenzofuran-5-ylsulfonyl)guanidino)pentanoic acid [ No CAS ]
[ 4688-76-0 ]
[ 82565-68-2 ]
Nα-(9-fluorenylmethyloxycarbonyl)-Nγ-2,2,4,6,7-pentamethyldihydrobenzofuran-5-sulfonyl-L-arginine [ No CAS ]
C₃₃H₄₄N₁₀O₃ [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2007,vol. 17,p. 2361 - 2364

8
[ 6781-98-2 ]
[ 4688-76-0 ]
2,6-dimethyl-2-phenyl-1,1'-biphenyl [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	With potassium phosphate; C48H54Cl2N5Pd; In water; isopropyl alcohol; at 45℃; for 15h;	General procedure: A mixture of aryl chloride (0.125 mmol), aryl boronic acid (0.15 mmol) and K4PO3 (0.25 mmol), catalyst (0.000125 mmol) in H2O (0.1 mL), isopropanol (0.1 mL) was stirred in a test tube at 45 C. After the reaction was completed, cooled to room temperature and the mixture was extracted with CH2Cl2 and dried over Na2SO4. The solvent was removed under vacuum. The product was purified by flash chromatography on a silica gel column. The characterization of all coupling products see Supporting Information.

Reference： [1]Journal of Organic Chemistry,2013,vol. 78,p. 11513 - 11524
[2]Chemical Communications,2011,vol. 47,p. 5079 - 5081
[3]Tetrahedron Letters,2019
[4]Angewandte Chemie - International Edition,2010,vol. 49,p. 5879 - 5883
[5]Tetrahedron,2007,vol. 63,p. 6879 - 6886

9
[ 106-38-7 ]
[ 4688-76-0 ]
[ 42984-87-2 ]

Reference： [1]Tetrahedron,2007,vol. 63,p. 9393 - 9400
[2]European Journal of Inorganic Chemistry,2008,p. 397 - 407
[3]Advanced Synthesis and Catalysis,2013,vol. 355,p. 421 - 438
[4]Patent: US2017/29278,2017,A1 .Location in patent: Sheet 3/8
[5]ARKIVOC,2012,vol. 2013,p. 228 - 248
[6]European Journal of Organic Chemistry,2015,vol. 2015,p. 3053 - 3056
[7]Organometallics,2017,vol. 36,p. 944 - 954
[8]Chemistry Letters,2013,vol. 42,p. 541 - 543

10
[ 131-09-9 ]
[ 4688-76-0 ]
[ 855004-46-5 ]

Yield	Reaction Conditions	Operation in experiment
94%	With caesium carbonate;tris-(dibenzylideneacetone)dipalladium(0); tricyclohexylphosphine; In 1,4-dioxane; toluene; at 80℃; for 10h;	Under the atmosphere of argon, 3.4 g (14 mmole) of 2-chloro-anthraquinone, 5 g (17 mmole, 1.2 eq) of 2-biphenylylboronic acid, 0.32 g (0.35 mmole; 5% by mass Pd) of tris(dibenzylideneacetone)dipalladium(0) and 14 g (43 mmole; 2.5 eq) of cesium carbonate were suspended in 40 ml of anhydrous dioxane. Then, 1.1 ml (25% by mass; 0.98 mmole; 1.4 eq to Pd) of a toluene solution of tricyclohexylphosphine was added, and the resultant mixture was stirred at 80 C. for 10 hours. The obtained reaction mixture was diluted with 100 ml of water and 300 ml of toluene, and insoluble components were removed by filtration with zeolite. The organic layer was separated from the filtrate, washed with 50 ml of a saturated aqueous solution of sodium chloride and dried with anhydrous magnesium sulfate. The solvent was removed by distillation, and a deep red oily substance was obtained. The obtained oily substance was purified in accordance with the column chromatography (the column packed with silica gel). The purification was conducted with a mixed solvent of hexane and 33% by mass of dichloromethane and then with a mixed solvent of hexane and 50% by mass of dichloromethane. After the purification, 7.1 g (the yield: 94%) of a light yellow solid substance was obtained. The obtained solid substance was identified to be Compound (A-1) described above in accordance with 1H-NMR and the field desorption mass analysis (FDMS). The results of the measurements of 1H-NMR and FDMS are shown in the following. 1H-NMR (CDCl3, TMS) delta: 7.18 (5H, s), 7.49 (5H, s), 7.76 (2H, dd, J=6 Hz, 3 Hz), 8.08 (1H, d, J=8 Hz), 8.2-8.3 (3H, m) FDMS calcd. for C26H16O2=360; found: m/z=360 (M+, 100)
94%	With caesium carbonate;tris-(dibenzylideneacetone)dipalladium(0); tricyclohexylphosphine; In 1,4-dioxane; toluene; at 80℃; for 10h;	(1) Synthesis of 2-(2-biphenylyl)-9,10-anthraquinone [Compound (A)]; Under an atmospheric argon gas flow, 2-chloroanthraquinone in an amount of 3.4 g (14 mmol), 2-biphenylylboronic acid in an amount of 5 g (17 mmol; 1.2 eq), tris(dibenzylideneacetone)dipalladium (0) in an amount of 0.32 g (0.35 mmol; 5 % Pd) and cesium carbonate in an amount of 14 g (43 mmol; 2.5 eq) are suspended into 40 milliliter of anhydrous dioxane, and adding a toluene solution of tricyclohexylphosphine in an amount 1.1 milliliter (25 % by mass, 0.98 mmol; 1.4 equivalent to Pd), the resultant solution was stirred at 80 C for 10 hours. The resultant reaction mixture was diluted with the use of water in an amount of 100 milliliter and further with the use of toluene in an amount of 300 milliliter and then, insolubles were filtrated by means of celite. An organic layer was separated from the filtrate and washed with the use of saturated sodium chloride solution in an amount of 50 milliliter and subsequently, dried with the use of sulfuric anhydride magnesium, followed by distillation of the solvent and as a result, deep red oil was obtained. The deep red oil was refined in accordance with column chromatography (filled with silicagel). The purification was carried out by eluting with the use of a mixed solvent of hexane and 33 % by mass of dichloromethane, followed by eluting with the use of mixed solvent of hexane and 50 % by mass of dichloromethane. As a result of the purification, 7.1 g of a pale brown solid compound was obtained (yield: 94 %). The pale brown solid was identified as the Compound (A) from the result in accordance with 1H-NMR and Field Desorption Mass Spectrum (FD-MS) measurement. The result of the measurement in accordance with 1H-NMR and FD-MS are shown as the following: 1H-NMR (CDCl3, TMS) delta 7.18(5H, s), 7.49 (5H, s), 7.76 (2H, dd, J=6Hz, 3Hz), 8.08 (1H, d, J=8Hz), 8.2-8.3 (3H, m) FDMS, calcd for C26H16O2=360, found m/z =360 (M+, 100)

Reference： [1]Patent: US2007/60777,2007,A1 .Location in patent: Page/Page column 17-18
[2]Patent: EP1695952,2006,A1 .Location in patent: Page/Page column 14

11
[ 2052-07-5 ]
[ 4688-76-0 ]

Yield	Reaction Conditions	Operation in experiment
		EXAMPLE 94A 2-(dihydroxyboryl)-1,1'-biphenyl The desired product was prepared by substituting 2-bromobiphenyl for 3-bromo-1,1'-biphenyl in Example 6A. MS (DCI/NH3) m/z 216 (M+NH4)+.

Reference： [1]Organic Letters,2011,vol. 13,p. 4479 - 4481
[2]New Journal of Chemistry,2012,vol. 36,p. 662 - 667
[3]Patent: US2002/19527,2002,A1
[4]RSC Advances,2013,vol. 3,p. 20666 - 20672
[5]Journal of Organic Chemistry,2015,vol. 80,p. 4532 - 4544

12
[ 144981-86-2 ]
[ 4688-76-0 ]
C₃₉H₃₀ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 80℃; for 8h;	1.27 g (2.8 mmole) of 2,7-diiode-(9,9- dimethyl) -fluorene, 1.24 g (6.26 mmole) of 2- biphenylboric acid, 328 mg of Pd(PPh3)4, 20 ml of toluene, 10 ml of ethanol, and 20 ml of a 2M aqueous solution of sodium carbonate were fed into a 100-ml .-round-bottomed flask, and the whole was stirred at 800C for 8 hours in a stream of nitrogen. After the completion of the reaction, the resultant was extracted with toluene, and the organic layer was dried with magnesium sulfate. After that, the drying EPO <DP n="76"/>agent was filtered and the solvent was distilled off. The residue was dissolved into chloroform, and the solution was separated and purified by means of alumina column chromatography, followed by recrystallization from toluene. The resultant crystal was vacuum-dried at 120C, and the resultant was sublimated and purified to give 925 mg of Exemplified Compound No. X-5 (65% yield).498.2 as M+ of the compound was observed by means of Matrix Assisted Laser Desorption/Ionization- Time of Flight Mass Spectrometry (MALDI-TOF MS) .In addition, the structure of the compound was identified by NMR measurement.1H NMR (CDCl3, 400 MHz) ? (ppm) :.7.59 (d, 2H), 7.52 (m, 2H), 7.44-7.39 (m, 6H), -7.24 (dd, 2H), 7.22-7.11 (m, 10H), 6.94 (d,'2H), 0.97 (s, 6H)Further, the compound had a glass transition temperature of 800C.

Reference： [1]Patent: WO2006/35997,2006,A1 .Location in patent: Page/Page column 74-75

13
[ 607739-64-0 ]
[ 4688-76-0 ]
C₆₉H₅₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 80℃; for 8h;	1 g (1.35 mmole) of Compound A, 672 mg (3.39 mmole) of 2-biphenylboric acid, 156 mg of Pd(PPh3)4,2.0 ml of toluene, 10 ml of ethanol, and 20 ml of a 2M aqueous solution of sodium carbonate were fed into a 100-ml round-bottomed flask, and the whole was stirred at 800C for 8 hours in a stream of nitrogen. After the completion of the reaction, the resultant was extracted with toluene, and the organic layer was dried with magnesium sulfate. After that, the drying agent was filtered and the solvent was distilled off. EPO <DP n="62"/>The residue was dissolved into chloroform, and the solution was separated and purified by means of alumina column chromatography, followed by recrystallization from toluene. The resultant crystal was vacuum-dried at 1200C, and the resultant was sublimated and purified to give 700 mg of Exemplified Compound No. X-25 (58% yield) .882.4 as M+ of the compound was confirmed by means of Matrix Assisted Laser Desorption/Ionization- Time of Flight Mass Spectrometry (MALDI-TOF MS) .In addition, the structure of the compound was identified by NMR measurement.1H NMR (CDCl3, 400 MHz) ? (ppm) : 7.82 (d, 4H), 7.77 (d, 4H), 7.69-7.62 (m, 20H), 7.57-7.53 (m, 4H), 7.49-7.43 (m, 12H), 7.29 (dd, 4H), 7.20-7.15 (m, 20H), 7.02 (d, 4H), 1.63 (s, 6H), 1.31 (s, 12H)Further, the compound had a glass transition temperature of 154C

Reference： [1]Patent: WO2006/35997,2006,A1 .Location in patent: Page/Page column 60-61

14
[ 6825-20-3 ]
[ 4688-76-0 ]
[ 910897-97-1 ]

Yield	Reaction Conditions	Operation in experiment
46%	With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In 1,2-dimethoxyethane; water; at 80℃; for 3.5h;	As an example of a material according to the invention, a synthetic method of a compound represented by formula (67) 9-{4-[3, 6-di(2-phenyl) phenyl-N-carbazolyl] phenyl} -10-phenylanthracene (hereinafter referred to as BPCzPA) below will be described. Note that 9-phenyl-10-(4-bromophenyl) anthracene is prepared in the manner shown in Example 1. [0220][0221]First, a synthetic method of 3,6-di(2-phenyl-phenyl)-carbazole will be shown below. A mixture of 3.25 g (10.0 mmol) 3,6-dibromocarbazole, 4.2 g (21.0 mmol) of o-biphenylboronic acid, 50 mg (0.21 mmol) of palladium acetate, 6.9 g (5.2 mmol) of potassium carbonate, water (25 mL), 308 mg (1.0 mmol) of tri(ortho-tolyl) phosphine, and 30 mL of dimethoxyethane is heated to reflux at 80 0C for 3.5 three hours. After the reaction, the solution is rinsed with water, aqueous layer is thereafter extracted with toluene, and it is rinsed together with the organic layer using saturated salt solution, and thereafter dried with magnesium sulfate. After natural filtration, the filtrate is condensed to obtain 2.2 g of 3, 6-di(2 -phenyl -phenyl)-carbazole as a white solid at a EPO <DP n="70"/>yield of 46 %. A synthetic scheme of 3,6-di(2-phenyl-phenyl)-carbazole is shown below.
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene;	Manufacturing Example 29 A solution was prepared by adding 6.50 g of 3,6-dibromocarbazole, 10.00 g of biphenyl-2-boronic acid, and 0.72 g of tetrakis(triphenylphosphine)palladium into 20 ml of ethanol and 100 ml of toluene. The resulting solution was blended with 40.g of a 22% aqueous solution of sodium carbonate, and the mixture was heated under reflux in a nitrogen atmosphere for 7.5 hours. After the mixture was cooled, toluene and water were added thereto, and insoluble materials were removed therefrom using a filter aid. Subsequently, the organic layer was separated from the aqueous layer, and the solvent was distilled off under a reduced pressure. After washing with water and drying were performed, so that a light brown powder was prepared. The resulting powder was subjected to a silica gel column chromatography treatment (eluant: toluene/hexane=2/1 on a volume ratio basis), followed by washing with ethanol. Thus, 5.22 g of a colorless needle crystal of 3,6-bis(2-biphenylyl)carbazole was produced. The physical properties thereof were as follows. melting point: 186.0C to 189.0 C. elemental analysis value (%) measured value/calculated value C 91.46/91.69 H 5.13/5.34 N 3.05/2.97 infrared absorption spectrum (KBr pellet-method) NH stretching vibration: 3425 cm-1

Reference： [1]Angewandte Chemie - International Edition,2020,vol. 59,p. 7813 - 7817
Angew. Chem.,2020,vol. 132,p. 7887 - 7891,5
[2]Patent: WO2006/104221,2006,A1 .Location in patent: Page/Page column 67-68
[3]Patent: US2005/84711,2005,A1

15
[ 27973-29-1 ]
[ 4688-76-0 ]
1,6-di(2-biphenyl)pyrene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 90℃; for 8h;	Under an atmospheric argon gas flow, 1,6-dibromopyrene in an amount of 9.7 g (27.0 millimole), 2-biphenylboronic acid in an amount of 12.8 g (64.8 millimole), tetrakis(triphenylphosphine)palladium(0) in an amount of 1.25 g (4 % by mole), sodium carbonate aqueous solution in an amount of 61 milliliter (122 millimole, 2M) and dimethoxyethane (DME) in an amount of 120 milliliter were placed into a three-neck flask equipped with a cooling pipe and having a capacity of 200 milliliter, and the resultant solution was stirred with heating at a temperature of 90 C for 8 hours. After the completion of the reaction, adding 50 milliliter of water, precipitated crystal was separated by filtration and washed with the use of 50 milliliter of water and 100 milliliter of ethanol, and as a result, 13.3 g of 1,6-di(2-biphenyl)pyrene (white powder) was obtained (the yield: 97 %). Subsequently, under an atmospheric argon gas flow, 1,6-di(2-biphenyl)pyrene in an amount of 13.2 g (26.1 millimole), N-bromosuccinimide in an amount of 9.8 g (55 millimole) and dried dimethylformamide (DMF) in an amount of 550 milliliter were placed into an eggplant flask equipped with a cooling pipe and having a capacity of 1 liter, and the resultant solution was stirred with heating at a temperature of 50 C for 8 hours. After the completion of the reaction, adding 300 milliliter of water, precipitated crystal was separated by filtration and washed with the use of 50 milliliter of water and 100 milliliter of methanol, and as a result, 10.5 g of pale yellow powder was obtained (the yield: 61 %). The pale yellow powder was identified as 1,6-di(2-biphenyl)-3,8- dibromopyrene from the result of 1H-NMR spectrum (refer to FIG. 4) and FD-MS measurement.

Reference： [1]Patent: EP1746080,2007,A1 .Location in patent: Page/Page column 10

16
[ 1052271-60-9 ]
[ 4688-76-0 ]
[ 1059098-59-7 ]

Yield	Reaction Conditions	Operation in experiment
13%	With sodium hydroxide;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; for 24.0h;Heating / reflux;	Example 18; 8-(biphen-2-yl)H-imidazo[1,5-a]pyridine8-bromo-H-imidazo[1,5-a]pyridine (0.1 g, 0.5 mmol, 1 eq) was dissolved in 10 mL of DME and kept under an argon atmosphere. To that solution [Pd(PPh3)4] (0.025 mmol, 0.05 eq), biphen-2-yl boronic acid (0.149 g, 0.75 mmol, 1.5 eq) and an aqueous NaOH solution (0.2M, 5 mL) were added under stirring. The resulting mixture was refluxed for 24 h. After cooling, the mixture was diluted with water and the aqueous layer was extracted with CHCl3. The organic layers were dried (Na2SO4), filtered and evaporated under reduced pressure. Semi-preparative HPLC-chromatography afforded the pure product.Yield: 0.018 g (13%), 1H-NMR, 500 MHz, CDCl3: delta 6.76 (dd, 1H); 6.85 (t, 1H); 7.06-7.13 (m, 5H); 7.24-7.25 (m, 1H), 7.39-7.53 (m, 4H); 8.02 (td, 1H); 9.13 (d, 1H), MS: m/z 271.6 [M+H]+; HPLC: Method [B]. (214 nm), rt: 8.99 min (99.7%)

Reference： [1]Patent: US2008/234313,2008,A1 .Location in patent: Page/Page column 30-31

17
[ 130507-37-8 ]
[ 4688-76-0 ]
[ 641611-79-2 ]

Yield	Reaction Conditions	Operation in experiment
58%	With triethylamine;dichlorobis(tri-O-tolylphosphine)palladium; In ethanol; at 90℃; for 2h;Heating / reflux;	Compound A (100 mg, 0.28 mmol) prepared in Reference Example 1, 2-biphenylboric acid (66 mg, 0.34 mmol) and bis(tri-o-tolylphosphine)palladium (II) dichloride (22 mg, 0.03 mmol) were dissolved in 4 mL of ethanol, and triethylamine (0.12 mL, 0.83 mmol) was added thereto. The mixture was heated and refluxed at 90C for approximately 2 hours. After completion of the reaction, the solvent was distilled off, and to the resulting residue was added 50 mL of a 2 mol/L sodium hydroxide aqueous solution and diethyl ether to wash the residure. After the aqueous layer was filtered, the filtrate was stirred under ice cooling, and acetic acid was slowly added dropwise to the solution to neutralize. Crystals precipitated were collected by filtration, and recrystallized from a DMF-water mixed solvent to obtain 70 mg of the title compound (compound C) as a white powder (yield 58%). 1H NMR (delta ppm, DMSO-d6): 8.13 (dd, J=5.7, 9.2 Hz, 1H), 7.70 (dt, J=3.0, 9.2 Hz, 1H), 7.51-7.45 (m, 8H), 7.29-7.17 (m, 7H), 2.36 (s, 3H) Mass (m/z): 434 (M+1) IR (KBr) : 3100, 2500, 1718, 1626, 1504, 1475, 1284, 1238, 1192, 1007, 989, 829, 750, 702 cm-1 m.p.: >300C

Reference： [1]Patent: EP1541149,2005,A1 .Location in patent: Page/Page column 26-27

18
[ 626-55-1 ]
[ 4688-76-0 ]
[ 911497-13-7 ]

Yield	Reaction Conditions	Operation in experiment
80.6%		According to the above reaction scheme, one equivalent biphenyl-2-boronic acid, 1.2 equivalents 3-bromopyridine and 3 mole-% tetrakis(triphenylphosphine)-palladium (0) were dissolved in a mixture of 3 L/mole of degassed toluene, 3 L/mole of degassed ethanol and 2 L/mole of degassed water in a round bottom flask under a nitrogen atmosphere. The mixture was stirred for 5 minutes at room temperature. Then, 3 equivalents of sodium carbonate were added to the mixture and the mixture was heated under reflux for 72 hours. Once the reaction mixture was cooled down, it was extracted four times with appropriate portions of CHCl3, the combined organic fractions were washed twice with appropriate amounts of 1 N solution of sodium hydroxide and twice with appropriate amounts of deionized water. The combined organic fractions were dried over magnesium sulfate and the crude product was flash chromatographed on silica gel (n-hexane:ethyl acetate, 2:1) and recrystallized from n-hexane. White crystals having a melting point of 76 C. were obtained, giving 80.6% yield.

Reference： [1]Patent: US2008/194821,2008,A1 .Location in patent: Page/Page column 8

19
[ 1092513-18-2 ]
[ 4688-76-0 ]
[ 1067883-76-4 ]

Reference： [1]Angewandte Chemie - International Edition,2008,vol. 47,p. 8059 - 8063
[2]Organic Syntheses,2016,vol. 92,p. 195 - 212

20
[ 545392-56-1 ]
[ 4688-76-0 ]
[ 1196133-45-5 ]

Yield	Reaction Conditions	Operation in experiment
77%		After the inside atmosphere of a 100 mL recovery flask was replaced with a nitrogen gas atmosphere, the following reagents and solvents were added thereto.7,7-dimethyl-5, 8-dibromodibenzo [c, g] fluorene: 0.6O g (1.33 mmol) 2-biphenyl boronic acid: 0.55 g (2.78 mmol) toluene: 20 ml ethanol: 10 mlNext, after adding 10 mL of a 10 wt% of an aqueous sodium carbonate solution, the reaction solution was stirred at room temperature for 30 minutes. Then, after adding 55 mg (0.078 mmol) of bis (triphenylphosphine) palladium (II) dichloride thereto, the reaction solution was stirred for 4 hours under heating and reflux. Upon the completion of the reaction, the organic layer was extracted with toluene, washed with water, and dried over anhydrous sodium sulfate. By concentrating the organic layer under reduced pressure, a crude product was obtained. Next, the thus obtained crude product was subjected to silica gel column chromatography (developing solvent: heptane/toluene = 4/1) . Subsequently, slurry washing under heating with a heptane/toluene mixed solvent and slurry washing under heating with an ethanol/chloroform mixed solvent were carried out sequentially followed by vacuum drying under heating at 1300C to give 610 mg of Exemplified Compound HA-19 (yield: 77%) .Identification of the thus obtained compound was carried out. Results are described below.[MALDI-TOF MS (Matrix Assisted Ionization - Time of Flight Mass Spectroscopy) ] Found value: m/z = 598.15; calculated value: C47H34 = 598.27 [1H-NMR (400MHz, CDCl3)] delta:8.69(t,2H) ,7.90 (t, 2H) , 7.65-7.45 (m, 10H) ,7.42-7.38 (m,2H) , 7.22 ( s, IH) ,7.16 (s, IH) , 7.11-6.95 (m, 10H) ,1.35(s,1.5H), 1.06(s, 3H) ,0.87 (s,1.5H).

Reference： [1]Patent: WO2009/139499,2009,A1 .Location in patent: Page/Page column 63-64

21
[ 1592-95-6 ]
[ 4688-76-0 ]
[ 1204427-20-2 ]

Yield	Reaction Conditions	Operation in experiment
61%	With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 80℃; for 2h;Inert atmosphere;	Into a 100 mL three-neck flask were put 0.50 g (2.0 mmol) of 3-bromo-9H-carbazole, 0.40 g (2.0 mmol) of 2-biphenylboronic acid, and 0.15 g (0.50 mmol) of tri(ortho-tolyl)phosphine, and the air in the flask was replaced with nitrogen. To the mixture were added 30 mL of toluene, 10 mL of ethanol, and 2.0 mL of a potassium carbonate solution (0.2 mol/L). This mixture was stirred to be degassed while the pressure was reduced. To the mixture was added 23 mg (0.10 mmol) of palladium(II) acetate , and the mixture was stirred at 80 0C under a nitrogen stream for 2 hours. After the stir, the aqueous layer was extracted with toluene and the extracted solution and the organic layer were washed together with saturated saline. The organic layer was dried with magnesium sulfate, and this mixture was subjected to gravity filtration. The obtained filtrate was concentrated to give a solid. The solid was dissolved in about 10 mL of toluene. The solution was subjected to suction filtration through Celite (Catalog No. 531-16855 manufactured by Wako Pure Chemical Industries, Ltd.), alumina, and Florisil (Catalog No. 540-00135 manufactured by Wako Pure Chemical Industries, Ltd.). The obtained filtrate was concentrated to give a white solid. The obtained white solid was recrystallized with a mixed solvent of toluene and hexane to give 0.40 g of white power, which was the object, at a yield of 61%. [0627] A synthetic scheme (E-I) of 3-(biphenyl-2-yl)-9H-carbazole is shown below.

Reference： [1]Patent: WO2010/5066,2010,A1 .Location in patent: Page/Page column 202-203

22
[ 1204427-12-2 ]
[ 4688-76-0 ]
[ 1204427-19-9 ]

Yield	Reaction Conditions	Operation in experiment
67%	With potassium carbonate; tris-(o-tolyl)phosphine;palladium diacetate; In ethanol; water; toluene; at 80℃; for 3h;Inert atmosphere;	In a 300 mL three neck flask were put 3.0 g (5.2 mmol) of 3-bromo-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole, 1.0 g (5.2 mmol) of 2-biphenylboronic acid, and 0.40 g (1.3 mmol) of tri(ortho-tolyl)phosphine. The atmosphere in the flask was replaced with nitrogen. To this mixture were added 60 mL of toluene, 20 mL of ethanol, and 5.0 mL of an aqueous potassium carbonate solution (2.0 mol/L). This mixture was stirred to be degassed while the pressure was reduced. To this mixture was added. 58 mg (0.26 mmol) of palladium(II) acetate.This mixture was stirred under a nitrogen stream at 80 C. for 3 hours. After being stirred, the mixture was separated into an aqueous layer and an organic layer. The aqueous layer was extracted with toluene. The extract and the organic layer were combined and washed with saturated brine. The organic layer was dried with magnesium sulfate, followed by gravity filtration of this mixture. An oily substance obtained by concentration of the resulting filtrate was dissolved in about 10 mL of toluene. This solution was suction filtered through Celite (manufactured by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), alumina, and Florisil (manufactured by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135). An oily substance obtained by concentration of the resulting filtrate was purified by silica gel column chromatography (the developing solvent was a mixed solvent of a 5:1 ratio of hexane to toluene) to give a light yellow oily substance. This light yellow solid obtained was recrystallized with a mixed solvent of toluene and hexane to give the desired substance as 2.0 g of a light yellow powder in a yield of 67%.Sublimation purification of 2.0 g of the light yellow powder obtained was performed by a train sublimation method. The light yellow powder was heated at 280 C. with an argon flow rate of 4.0 mL/min under reduced pressure. After the sublimation purification, 1.9 g of a light yellow solid which was the desired substance was obtained in a yield of 93%. By a nuclear magnetic resonance (NMR) method, this compound was confirmed to be 3-(biphenyl-2-yl)-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPAoB) which was the desired compound.The following are data of the 1H NMR measurement of the compound obtained: 1H NMR (DMSO-d6, 300 MHz):delta=7.14-7.27 (m, 6H), 7.33 (t, J=7.5 Hz, 1H), 7.45-7.81 (m, 22H), 7.87 (d, J=8.1 Hz, 2H), 8.21 (d, J=9.0 Hz, 2H)In addition, FIGS. 22A and 22B show 1H NMR charts. Note that FIG. 22B is a chart showing an enlarged part in the range of 7.0 ppm to 8.5 ppm in FIG. 22A.
	With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 80℃; for 3h;Inert atmosphere;	Into a 300 mL three-neck flask were put 3.0 g (5.2 mmol) of 3-bromo-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole, 1.0 g (5.2 mmol) of 2-biphenylboronic acid, and 0.40 g (1.3 mmol) of tri(ortho-tolyl)phosphine, and the air in the flask was replaced with nitrogen. To the mixture were added 60 mL of toluene, 20 mL of ethanol, and 5.0 mL of a potassium carbonate solution (0.2 mol/L). This mixture was stirred to be degassed while the pressure was reduced. After the degassing, the air in the flask was replaced with nitrogen. Then, to the mixture was added 58 mg (0.26 mmol) of palladium(II) acetate. The mixture was stirred at 80 C under a nitrogen stream for 3 hours. After the stir, the aqueous layer of the mixture was extracted with toluene and the extracted solution and the organic layer were washed together with saturated saline. The organic layer was dried with magnesium sulfate, and this mixture was subjected to gravity filtration. The obtained filtrate was concentrated to give an oily substance. The oily substance was dissolved in about 10 mL of toluene. The solution was subjected to suction filtration through Celite (Catalog No. 531-16855, manufactured by Wako Pure Chemical Industries, Ltd.), alumina, and Florisil (Catalog No. 540-00135, manufactured by Wako Pure Chemical Industries, Ltd.). The obtained filtrate was concentrated to give an oily substance. The obtained oily substance was purified by silica gel column chromatography (a developing solvent was a mixed solvent of hexane and toluene (hexane: toluene= 5: I)) to give a light yellow oily substance. The obtained light yellow oily substance was recrystallized with a mixed solvent of toluene and hexane to give 2.0 g of light yellow powder, which was the object, at a yield of 67%.[0648]Sublimation purification by train sublimation was performed on 2.0 g of the obtained light yellow powder. The sublimation purification was performed under such conditions that the light yellow powder was heated at 280 0C with an argon gas applied at a flow rate of 4.0 mL/min under reduced pressure. After the sublimation purification, 1.9 g of a light yellow solid, which was the objective compound, was recovered in 93% yield. [0649]As in Synthesis Example 1 of CzPAoB, this compound was found to be 3-(biphenyl-2-yl)-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (CzPAoB), which was the object, by nuclear magnetic resonance (NMR).

Reference： [1]Patent: US2010/76201,2010,A1 .Location in patent: Page/Page column 36-37
[2]Patent: WO2010/5066,2010,A1 .Location in patent: Page/Page column 207-209

23
[ 890148-78-4 ]
[ 4688-76-0 ]
[ 1201800-84-1 ]

Reference： [1]Journal of Materials Chemistry,2009,vol. 19,p. 8112 - 8118

24
[ 2398-37-0 ]
[ 4688-76-0 ]
[ 929700-46-9 ]

Yield	Reaction Conditions	Operation in experiment
90%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; for 8h;Reflux; Inert atmosphere;	(A-1) Synthesis of 3-methoxy[1,1':2',1 "]terphenyl Under an argon atmosphere, 18.7 g of 3-bromoanisole, 23.8 g of 2-biphenylboronic acid and 2.31 g of tetraxis(triphenylphosphine)palladium(0) were placed in a flask. 340 mL of dimethyl ether (DME) and 170 mL of a 2M aqueous sodium carbonate solution were added to this flask, and the resultant was refluxed with stirring while heating for 8 hours. After cooling to room temperature, an aqueous phase was removed. An organic phase was washed with water and saturated brine, and then dried with magnesium sulfate. After the magnesium sulfate was filtered out, the organic phase was concentrated. The resulting residue was purified by means of silica gel column chromatography, whereby 23.4 g (yield: 90%) of intended 3-methoxy[1,1':2',1"]terphenyl was obtained.

Reference： [1]Patent: EP2213641,2010,A1 .Location in patent: Page/Page column 30

25
[ 576-83-0 ]
[ 4688-76-0 ]
[ 1246888-96-9 ]

Yield	Reaction Conditions	Operation in experiment
95%	With potassium phosphate; 4-(2,6-dimethoxyphenyl)-3-(1,1-dimethylethyl)-2,3-dihydro-1,3-benzoxaphosphole;tris-(dibenzylideneacetone)dipalladium(0); In toluene; at 70℃;Inetrt atmosphere;	To a mixture of biphenyl-2-ylboronic acid (0.15 g, 0.75 mmol, 1.5 equiv) and 2-bromo- 1,3,5-trimethylbenzene (100 mg, 0.5 mmol, 1.0 equiv),tris(dibenzylideneacetone)dipalladium (0.46 mg, 0.0005 m mol, 0.1 mol %), 3-tert-butyl-4- (2,6-dimethoxyphenyl)-2,3-dihydrobenzo[if\|[l,3]oxaphosphole (0.66 mg, 0.04 mmol, 0.4 mol %), and potassium phosphate (0.318 g, 1.5 mmol, 3 equiv) was charged dagassed toluene (4 mL). The mixture was stirred at 70 C under nitrogen for 3 h, then quenched with water (4 mL). The organic phase was separated, washed with brine, dried over sodium sulfate, concentrated, and purified by column chromatography to provide pure desired product as oil (129 mg, 0.48 mmol, 95%). ESI-MS: m/z 273 [M +H]+.

Reference： [1]Angewandte Chemie - International Edition,2010,vol. 49,p. 5879 - 5883
[2]Patent: WO2011/126917,2011,A1 .Location in patent: Page/Page column 17

26
[ 4688-76-0 ]
[ 99-90-1 ]
[ 5173-05-7 ]

Yield	Reaction Conditions	Operation in experiment
98%	With potassium carbonate;solid phase supported palladium catalyst; In ethanol; water; at 20℃; for 0.5h;	[Reaction Example 2]4-Bromoacetophenone (100 mg, 0.50 mmol), 2-phenylphenylboronic acid (138 mg, 0.70 mmol, 1.4 eq.), potassium carbonate (139 mg, 1.0 mmol, 2.0 eq.), the palladium catalyst (8 mg, 0.005 mmol, 0.01 eq.), and 50% aq. ethanol (2.0 mL) were added in a test tube of 10 mL, and stirring at room temperature was started. After stirring for 30 min, the reaction was stopped, and the catalyst was separated with a centrifuge, then isolation and purification were carried out by decantation with diethyl ether/ethanol, a short column (ethyl acetate/n-hexane=1/3), and a column (ethyl acetate/n-hexane=1/10), then the intended substance represented in the following formula was obtained (134 mg, 98%).

Reference： [1]Synlett,2011,p. 2545 - 2550
[2]Synlett,2010,p. 1990 - 1996
[3]Patent: US2012/232310,2012,A1 .Location in patent: Page/Page column 6

27
[ 72141-44-7 ]
[ 4688-76-0 ]
[ 1255519-78-8 ]

Yield	Reaction Conditions	Operation in experiment
76.5%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate monohydrate;tris-(dibenzylideneacetone)dipalladium(0); In water; toluene; for 18h;Inert atmosphere; Reflux;	Step 1. Synthesis of 4-(biphenyl-2-yl)-2-methoxypyridine. A nitrogen flushed mixture of <strong>[72141-44-7]4-chloro-2-methoxypyridine</strong> (3.0 g, 21.03 mmol), 2-biphenylboronic acid 5.0 g, 25.23 mmol), Pd2(dba)3 (381 mg, 0.414 mmol), 2-dicyclohexylphosphino-2',6'- dimethoxybiphenyl (681 mg, 1.66 mmol), toluene (250 mL) and a slurry OfK3PO4H2O (14.57 g, 63.09 mmol) in water (25 mL) were refluxed for 18 h. After the mixture cooled to room temperature the organic layer was dried over anhydrous Na2SO4, filtered, and concentrated in vacuum. The residue was purified by flash chromatography on silica (hexane: ethyl acetate) and recrystallized from ethyl acetate to give 4-(biphenyl-2-yl)-2- methoxypyridine (4.2 g, 76.5%).

Reference： [1]Patent: WO2010/132524,2010,A1 .Location in patent: Page/Page column 59

28
[ 16789-84-7 ]
[ 4688-76-0 ]
[ 1260146-91-5 ]

Reference： [1]Organic Letters,2011,vol. 13,p. 26 - 29

29
[ 4688-76-0 ]
[ 501-65-5 ]
[ 602-15-3 ]

Yield	Reaction Conditions	Operation in experiment
81%	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; copper(II) acetate monohydrate; In N,N-dimethyl-formamide; at 100℃; for 2h;	General procedure: To a 20 mL two-necked flask were added arylboronic acid 1 (0.25 mmol), alkyne 2 (0.25 mmol), [(Cp*RhCl2)2] (0.005 mmol,3 mg), Cu(OAc)2·H2O (0.025 mmol, 5 mg), 1-methylnaphthalene (ca. 50 mg) as internal standard, and DMF (3 mL). The resulting mixture was stirred under air at 100C for 2 h. Then, the reaction mixture was cooled to room temperature and filtered through an alumina pad with CH2Cl2. After evaporating the solvents, product 3 was isolated by column chromatography on silica gel.

Reference： [1]Synlett,2016,vol. 27,p. 1707 - 1710
[2]Angewandte Chemie - International Edition,2019,vol. 58,p. 6342 - 6346
Angew. Chem.,2019,vol. 131,p. 6408 - 6412,5
[3]Journal of Organic Chemistry,2011,vol. 76,p. 2867 - 2874

30
[ 4688-76-0 ]
[ 90-43-7 ]

Yield	Reaction Conditions	Operation in experiment
86%	With oxygen; triethylamine; In 2-methyltetrahydrofuran; at 20℃; under 760.051 Torr; for 48h;UV-irradiation;	General procedure: [1,1'-Biphenyl] -4-phenylboronic acid (59.4mg, 0.3mmol, 1.0equiv) was added to a dried 20mL quartz test tube,Vacuum the quartz test tube while backfilling with oxygen three times.Under oxygen conditions, Et3N (62.5 L, 0.45 mmol, 1.5 equiv) and 2-methyltetrahydrofuran (4 ml) were sequentially added through a syringe.The resulting mixture was stirred for 5 minutes, then the quartz test tube was transferred to a photoreactor.The test tube was placed about 2 cm from the 15W UV lamp.The reaction mixture was stirred and illuminated for 24 h,After the specified time, the crude product was diluted with ethyl acetate, filtered through a pad of silica gel, and concentrated under reduced pressure.Flash chromatography on silica gel was then performed directly on silica gel (EtOAc / PE = 1/10) to give the desired product 1b (92% yield, white solid).
	With choline chloride; dihydrogen peroxide; In water; at 20℃;Green chemistry;	General procedure: A mixture of arylboronic acid (1.0mmol), 30% H2O2 (5equiv, 0.5mL), water (2mL) and ChCl/ HFIP (10mol%, 2 drops) was stirred at room temperature for the time indicated in Scheme 2. After completion of the reaction (indicated by TLC), the reaction mixture was extracted with EtOAc (3×10mL). The organic layer was concentrated and the resulting crude products were purified by column chromatography on silica gel using PE/EtOAc as eluent to provide the desired products.

Reference： [1]Advanced Synthesis and Catalysis,2018,vol. 360,p. 2013 - 2019
[2]Organic Letters,2012,vol. 14,p. 3494 - 3497
[3]European Journal of Organic Chemistry,2013,p. 7291 - 7294
[4]Green Chemistry,2019,vol. 21,p. 4971 - 4975
[5]Patent: CN110668921,2020,A .Location in patent: Paragraph 0025-0028; 0030-0032
[6]Organic Letters,2018,vol. 20,p. 4979 - 4983
[7]European Journal of Inorganic Chemistry,2011,p. 3232 - 3239
[8]Journal of Fluorine Chemistry,2014,vol. 158,p. 44 - 47

31
[ 16292-17-4 ]
[ 4688-76-0 ]
[ 1222634-01-6 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; for 15h;Reflux;	Preparation Example 23 (Synthesis of Intermediate Am9) In an argon gas stream, 750ml of toluene and 300ml of 2M sodium carbonate aqueous solution were added to a mixture of 32.7g (100mmol) of <strong>[16292-17-4]bis(4-bromophenyl)amine</strong>, 41.6g (210mmol) of 2-biphenyl boronic acid and 1.15g (1.00mmol) of tetrakis(triphenylphosphine)palladium(0). The mixture was heated under reflux for 15 hours. The solution was filtrated immediately after the reaction, and then the aqueous phase was removed. The organic phase was dried over magnesium sulfate and concentrated, and the residue was purified by column chromatography on silica gel to give 30.3g of glassy solid. FD-MS analysis identified the solid as Intermediate Am9.

Reference： [1]Patent: EP2348017,2011,A1 .Location in patent: Page/Page column 51

32
[ 1229012-68-3 ]
[ 4688-76-0 ]
[ 625121-77-9 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium phosphate;tris-(dibenzylideneacetone)dipalladium(0); tricyclohexylphosphine; In 1,4-dioxane; water; at 80 - 100℃;Inert atmosphere;	Example 4; This example illustrates the preparation of phenanthroline derivative Compound 9, using Suzuki coupling of <strong>[1229012-68-3]2,9-dichloro-4,7-diphenyl-1,10-phenanthroline</strong> from Example 1 with the boronic ester shown below. Take 2.0 g of dichloro-phen (5 mM) in glove box and add 2.0 g (11 mM) boronic ester (Aldrich). Add 0.15 g Pd2 DBA3 (0.15 mM), 0.1 g tricylohexylphosphine (0.35 mM) and 3.75 g potassium phosphate (17 mM) and dissolve all into 30 mL dioxane and 15 mL water. Mix and heat in glove box in mantle at 100 C for 1 hr then warm gently (minimum rheostat setting) under nitrogen overnight. Solution immediately is dark purple but on reaching 80 C it is a tan brown slurry which slowly becomes clear brown. As the solution cools a flocculent ppt forms. Cool and work up by removing from glove box and adding more water. Separate the aqueous and organic layers and wash aq layer with DCM. Combine all organic layers, dry on anhydrous magnesium sulfate and filter through a silica plug. Collect the orange solution which was evaporated to low volume and methanol was added to ppt a pale orange solid. Dissolve in hot toluene and run through a florisil column eluting a pale yellow band with toluene and then DCM. Evaporate to low volume and add methanol to ppt a crystalline white solid. Isolate 2.55 g material. The structure was confirmed by NMR analysis as Compound 9

Reference： [1]Patent: US2012/65402,2012,A1 .Location in patent: Page/Page column 14-15

33
[ 109179-31-9 ]
[ 4688-76-0 ]
3-methyl-2-(2-phenylphenyl)benzaldehyde [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2013,vol. 135,p. 18815 - 18823
[2]Organic Letters,2012,vol. 14,p. 3550 - 3553

34
[ 327-51-5 ]
[ 4688-76-0 ]
[ 1380586-82-2 ]

Reference： [1]Journal of Organic Chemistry,2012,vol. 77,p. 5445 - 5448

35
[ 4688-76-0 ]
[ 33332-28-4 ]
[ 1454654-41-1 ]

Yield	Reaction Conditions	Operation in experiment
63.02%	With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In ethanol; toluene; at 130℃; for 1h;Microwave irradiation;	6-biphenyl-2- l-pyrazin-2-ylamine To a solution of 2-amino-6-chloro-pyrazine (0.25 g, 1.93 mmol) in toluene / ethanol (9:1 , 10 ml), 2-biphenyl boronic acid (0.42 g, 2.13 mmol), tetrakis(triphenylphosphine)palladium(0) (0.067 g, 0.05 mmol) and cesium carbonate (1.25 g, 3.87 mmol) are added, degassed briefly and irradiated in microwave at 130 °C for an hour. The reaction mixture is passed through celite, washed with dichloromethane/methanol (1 :1 , 25 ml), the filtrate is concentrated and purified by silica column using (230-400) mesh to get the product as yellow solid (0.3 g, 63.02 percent); TLC: chloroform/methanol (9.5/0.5) Rf - 0.3. 1H NMR: 400 MHz, DMSO-d6: delta [ppm] 7.68 (s, 1 H), 7.58-7.55 (m, 1 H), 7.44- 7.51 (m, 2H), 7.39-7.41 (m, 1 H), 7.23-7.32 (m, 3H), 7.12-7.15 (m, 3H), 6.42 (br s, 2H); LCMS: Mass found (M+, 248.3) Method: A-0.1 percent TFA in H20, B-0.1percent TFA in ACN: Flow - 0.6 ml/min. Column: XBridge C8 (50 X 4.6 mm, 3.5 pm), +ve mode Rt (min): 3.54 area percent -98.72 (Max).

Reference： [1]Patent: WO2013/131609,2013,A1 .Location in patent: Page/Page column 125

36
[ 4688-76-0 ]
[ 54881-49-1 ]
[ 1510683-12-1 ]

Reference： [1]Journal of the American Chemical Society,2013,vol. 135,p. 18815 - 18823

37
[ 56518-42-4 ]
[ 4688-76-0 ]
[ 92-52-4 ]

Yield	Reaction Conditions	Operation in experiment
80%	With dichlorido[2-(1-methyl-4,5-diphenyl-1H-imidazol-2-yl)pyridine]palladium(II); potassium carbonate; In ethanol; water; for 0.5h;Reflux;	General procedure: Aryl bromide (1mmol), arylboronic acid (1.2mmol), potassium carbonate (1.5mmol), and palladium complex (0.2mol%) were placed in a 10mL round-bottom flask equipped with magnetic stirrer bar. Upon addition of ethanol (3mL) and deionized water (1mL), a clear solution was obtained which was then refluxed for the desired reaction time. After cooling, an aliquot of the reaction mixture was taken and washed slowly into an NMR tube over a short bed of anhydrous sodium sulfate with the aid of deuterated chloroform in order to minimize residual water from the reaction mixture. The reactivity of the pre-catalysts was evaluated by comparison of the NMR signals observed for the methylene protons of (4-bromophenyl)methanol (H1) and the corresponding product formed. The yield was calculated from the integral of the product peak as a percentage of the sum of all observed methylene signals.

Reference： [1]Journal of Organometallic Chemistry,2014,vol. 754,p. 39 - 50

38
[ 28320-32-3 ]
[ 4688-76-0 ]
[ 881911-62-2 ]

Yield	Reaction Conditions	Operation in experiment
63%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; at 100℃; for 12h;Inert atmosphere;	Synthesis of 2-(biphenyl-2-yl)-7-bromo-9,9-dimethyl-9H-fluorene A mixture of 35.2 g (100 mmol) of 2,7-dibromo-9,9-dimethyl-9H-fluorene, 21.8 g (110 mmol) of biphenyl-2-ylboronic acid, 2.31 g (2 mmol) of Tetrakis(triphenylphosphine) Palladium, 75 nm of 2M Na2CO3, 150 ml of EtOH and 300 ml toluene was degassed and placed under nitrogen, and then heated at 100 C. for 12 h. After the reaction finish, the mixture was allowed to cool to room temperature. The organic layer was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica (hexane-dichloromethane) to give product (26.8 g, 63.0 m mol, 63%) as a white solid. 1H NMR (CDCl3, 400 MHz): delta 7.61 (d, J=7.8 Hz, 1H), 7.55?7.53 (m, 2H), 7.49?7.42 (m, 5H), 7.29 (d, J=8.0 Hz, 1H), 7.20?7.14 (m, 5H), 6.98 (s, 1H), 1.21 (s, 6H)
63%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; at 100℃; for 12h;Inert atmosphere;	Synthesis of 2-(biphenyl-2-yl)-7-bromo-9,9-dimethyl-9H-fluorene A mixture of 35.2 g (100 mmol) of 2,7-dibromo-9,9-dimethyl-9H-fluorene, 21.8 g (110 mmol) of biphenyl-2-ylboronic acid, 2.31 g (2 mmol) of Tetrakis(triphenylphosphine)palladium, 75 ml of 2M Na2CO3, 150 ml of EtOH and 300 ml toluene was degassed and placed under nitrogen, and then heated at 100 C. for 12 h. After finishing the reaction. The mixture was allowed to cool to room temperature. The organic layer was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica (hexane-dichloromethane) to give product (26.8 g, 63.0 mmol, 63%) as a white solid. 1H NMR (CDCl3, 400 MHz): delta 7.61 (d, J=7.8 Hz, 1H), 7.55?7.53 (m, 2H), 7.49?7.42 (m, 5H), 7.29 (d, J=8.0 Hz, 1H), 7.20?7.14 (m, 5H), 6.98 (s, 1H), 1.21 (s, 6H)
63%	With tetrakis(triphenylphosphine) palladium(0); In ethanol; toluene;	Synthesis of 2-(biphenyl-2-yl)-7-bromo-9,9-dimethyl-9H-fluorene A mixture of 35.2 g (100 mmol) of 2,7-dibromo-9,9-dimethyl-9H-fluorene, 21.8 g (110 mmol) of biphenyl-2-ylboronic acid, 2.31 g (2 mmol) of tetrakis(triphenylphosphine)palladium, 75 ml of 2M Na2CO3, 150 ml of EtOH and 300 ml toluene was degassed and placed under nitrogen, and then heated at 100 C. for 12 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The organic layer was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica(hexane-dichloromethane) to give product (26.8 g, 63.0 mmol, 63%) as a white solid. 1H NMR (CDCl3, 400 MHz): chemical shift (ppm) 7.61 (d, J=7.8 Hz, 1H), 7.55?7.53 (m, 2H), 7.49?7.42 (m, 5H), 7.29 (d, J=8.0 Hz, 1H), 7.20?7.14 (m, 5H), 6.98 (s, 1H), 1.21 (s, 6H)

63%	In ethanol; toluene;	Example 1 Synthesis of 2-(biphenyl-2-yl)-7-bromo-9,9-dimethyl-9H-fluorene A mixture of 35.2 g (100 mmol) of 2,7-dibromo-9,9-dimethyl-9H-fluorene, 21.8 g (110 mmol) of biphenyl-2-ylboronic acid, 2.31 g (2 mmol) of Pd(PPh3)4, 75 ml of 2M Na2CO3, 150 ml of EtOH and 300 ml toluene was degassed and placed under nitrogen, and then heated at 100 C. for 12 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The organic layer was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica to give product (26.8 g, 63.0 mmol, 63%) as a white solid.
63%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; at 100℃; for 12h;Inert atmosphere;	The 35.2g (100mmol) 2,7-dibromo-9,9-dimethyl-9H-fluorene, 21.8g (110mmol) biphenyl-2-ylboronic acid, 2.31g (2mmol) Pd(PPh3)4, 75ml 2M Na2CO3, into a mixture of 300ml toluene 150ml EtOH degassed and placed under a nitrogen atmosphere, and then heated at 100 deg. C 12 hours. After completion of the reaction, the mixture was cooled to room temperature. The organic layer was extracted with ethyl acetate and water, dried over anhydrous magnesium sulfate, and the solvent was removed by column chromatography on silica gel, the residue was purified to give the product as a white solid (26.8g, 63.0mmol, 63%).
63%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; at 100℃; for 12h;Inert atmosphere;	A mixture of 35.2 g (100 mmol) of 2,7-dibromo-9,9-dimethyl-9H-fluorene, 21.8 g (110 mmol) of biphenyl-2-ylboronic acid, 2.31 g (2 mmol) of Pd(PPh3)4, 75 ml of 2M Na2CO3, 150 ml of EtOH and 300 ml toluene was degassed and placed under nitrogen, and then heated at 100 C. for 12 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The organic layer was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica to give product (26.8 g, 63.0 mmol, 63%) as a white solid.
63%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; at 100℃; for 12h;Inert atmosphere;	A mixture of 35.2 g (100 mmol) of 2,7-dibromo-9,9-dimethyl-9H-fluorene, 21.8 g (110 mmol) of biphenyl2-ylboronic acid, 2.31 g (2 mmol) of Pd(PPh3)4, 75 ml of 2M Na2CO3, 150 ml of EtOH and 300 ml toluene was degassed and placed under nitrogen, and then heated at 1000 C. for 12 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The organic layer was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica to give product (26.8 g, 63.0 mmol, 63%) as a white solid.
63%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; at 100℃; for 12h;Inert atmosphere;	Synthesis of 2-(biphenyl-2-yl)-7-bromo-9,9-dimethyl-9H-fluorene A mixture of 35.2 g (100 mmol) of 2,7-dibromo-9,9-dimethyl-9H-fluorene, 21.8 g (110 mmol) of 2-biphenylboronic acid, 2.31 g (2 mmol) of Pd(PPh3)4, 75 ml of 2 M Na2CO3, 150 ml of EtOH, and 300 ml of toluene was degassed and placed under nitrogen, and then heated at 100 C. for 12 hrs. After the reaction finished, the mixture was allowed to cool to room temperature. The organic layer was extracted with ethyl acetate and water, and then dried with anhydrous magnesium sulfate. Subsequently, the solvent was removed and then the residue was purified by column chromatography on silica to give the product (26.8 g, 63.0 mmol, 63%) as a white solid.

Reference： [1]Patent: US2014/131664,2014,A1 .Location in patent: Paragraph 0019-0020
[2]Patent: US2014/151645,2014,A1 .Location in patent: Paragraph 0017-0019
[3]Patent: US9048437,2015,B2 .Location in patent: Page/Page column
[4]Patent: US2015/214492,2015,A1 .Location in patent: Page/Page column
[5]Patent: CN105732594,2016,A .Location in patent: Paragraph 0136; 0137
[6]Patent: US2016/351835,2016,A1 .Location in patent: Paragraph 0034
[7]Patent: US2017/84842,2017,A1 .Location in patent: Paragraph 0015; 0016
[8]Patent: US2019/194534,2019,A1 .Location in patent: Paragraph 0022-0023

39
[ 1333240-17-7 ]
[ 4688-76-0 ]
2-(2-biphenyl)-4,5-dimethoxypyrimidine [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2014,vol. 57,p. 8086 - 8098

40
[ 51050-54-5 ]
[ 4688-76-0 ]
C₂₁H₁₄O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; ruphos; In water; N,N-dimethyl-formamide; at 80℃; for 0.5h;Inert atmosphere; Sealed tube;	General procedure: A sealed tube containing PdCl2(PPh3)2 (38.96mg, 0.055mmol, and 5mol%), Ruphos (5mol%) 3-chloroisochromen-1-one 1a (200.45mg, 1.11mmol), arylboronic acid 2a (1.22mmol), and K2CO3 (306.82mg, 2.22mmol) were purged with nitrogen gas three times. Then, DMF (3.00mL) was added with a syringe. The reaction mixture was stirred at 80C for 30min and was diluted with ethyl acetate (30mL). The mixture was filtered through a Celite bed and washed with ethyl acetate. The filtrate was concentrated under reduced pressure and the residue was purified on a silica gel column using hexane/ethyl acetate as eluent to afford the desired product, 3a.See Supporting document for spectral data of compounds 3a-zb and 4a-c

Reference： [1]Tetrahedron Letters,2015,vol. 56,p. 941 - 945

41
3-chloro-6,7-dimethoxy-1H-isochromen-1-one [ No CAS ]
[ 4688-76-0 ]
C₂₃H₁₈O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; ruphos; In water; N,N-dimethyl-formamide; at 80℃; for 0.5h;Inert atmosphere; Sealed tube;	General procedure: A sealed tube containing PdCl2(PPh3)2 (38.96mg, 0.055mmol, and 5mol%), Ruphos (5mol%) 3-chloroisochromen-1-one 1a (200.45mg, 1.11mmol), arylboronic acid 2a (1.22mmol), and K2CO3 (306.82mg, 2.22mmol) were purged with nitrogen gas three times. Then, DMF (3.00mL) was added with a syringe. The reaction mixture was stirred at 80C for 30min and was diluted with ethyl acetate (30mL). The mixture was filtered through a Celite bed and washed with ethyl acetate. The filtrate was concentrated under reduced pressure and the residue was purified on a silica gel column using hexane/ethyl acetate as eluent to afford the desired product, 3a.See Supporting document for spectral data of compounds 3a-zb and 4a-c

Reference： [1]Tetrahedron Letters,2015,vol. 56,p. 941 - 945

42
[ 75-89-8 ]
[ 4688-76-0 ]
2-(2,2,2-trifluoroethoxy)-1,1'-biphenyl [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With dmap; oxygen; copper(II) acetate monohydrate; at 40℃; for 1h;	General procedure: An oven-driedreaction flask, equipped with a reflux condenser, was charged with Cu(OAc)2·H2O (9.98mg, 0.05mmol, 10%), DMAP (122.2mg,1.0mmol, 2.0equiv), aryl(hetero) boronic acid or boronic acid pinacol esters (0.5mmol,1.0 equiv) and the mixture was flushed three times with oxygen. Trifluoroethanol (3ml) was added and thereaction mixture was stirred at 40oC for 1 hours or 80oCfor 3 hours. After cooling to room temperature, the reaction mixture wasfiltered through a plug of silica gel to remove the catalyst, DMAP and any insolublebyproducts, and the silica gel was washed with ethyl acetate. The solvent wasconcentrated in vacuo to afford the crude product which was purified by columnchromatography. The products were characterized by 1H NMR, 13CNMR, 19FNMR and GC-MS.
35%	With pyridine; copper diacetate; sodium carbonate; In dichloromethane; at 20℃; for 18h;	Example 6Phenylboronic acid with trifluoroethanol having various substituents in the divalent copper salt catalyzed coupling reaction.In dichloromethane (5ml) as a solvent, is added having different substituents phenylboronic acid (0.5mmol),Trifluoroethanol (1.0mmol), sodium carbonate (1.0 mmol) and pyridine (1.0mmol), the divalent copper salt Cu(OAc)2 (0.05mmol) catalyst, [silver carbonate (0.4mmol) / nitrogen atmosphere] was stirred at room temperature under an air atmosphere or 18 hours. By 19FNMRThe reaction was followed until the reaction was complete. Filtered, and the solvent was removed by column chromatography to give the corresponding aryl-trifluoroethoxyEther compounds.
35%	With pyridine; copper diacetate; sodium carbonate; In 1,2-dichloro-ethane; at 20℃; for 14h;Schlenk technique; Molecular sieve; Sealed tube;	General procedure: In a nitrogen-filled glove box, a 25 mL Schlenk tube equipped with a magnetic stir bar was charged with Cu(OAc)2 (9.3 mg,0.05 mmol, 0.1 equiv), aryl boronic acid 1 (0.5 mmol, 1.0 equiv),Na2CO3 (106.0 mg, 1.0 mmol, 2.0 equiv) and 4 A MS (250.0 mg). The vessel was sealed with a septum before removing from the glovebox. The tube was evacuated and backfilled with air for 3 times.Then DCE (5.0 mL), pyridine (39.6 mg, 0.5 mmol, 1.0 equiv) and CF3CH2OH (100.0 mg, 1.0 mmol, 2.0 equiv) were added respectivelyvia syringe. The mixture was stirred vigorously under a balloon ofair at room temperature for 14 h. Then the reaction solution was vacuum-filtered over a sintered-glass funnel with a tightly packedpad of Celite (1 cm thick), and the filter cake was rinsed with DCM(20 mL). The combined filtrates were concentrated. The residue was purified with silica gel column chromatography to provide the desired product.

Reference： [1]Tetrahedron Letters,2015,vol. 56,p. 4815 - 4818
[2]Patent: CN105348048,2016,A .Location in patent: Paragraph 0057; 0058; 0059; 0060;
[3]Journal of Fluorine Chemistry,2017,vol. 196,p. 24 - 31

43
[ 4688-76-0 ]
[ 45738-35-0 ]
4-([1,1′-biphenyl]-2-yl)-1H-indene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In 1,4-dioxane; water; at 80℃;	[00187] 4- fl.1 '-Biphenyll-2-yl)-lH-indene (h): A mixture of compound d (40 g, 205 mmol, 1 equiv), (biphenyl-2-yl)boronic acid (81.2 g, 410 mmol, 2 equiv), powdered potassium carbonate (85 g, 615 mmol, 3 equiv), and bis(triphenylphosphine)palladium(II)dichloride (7.2 g, 10.3 mmol, 0.05 equiv), 1,4-dioxane (300 mL) and water (150 mL) was heated overnight at 80C. The reaction was poured into 500 mL of water and extracted with ethyl acetate (3 x 400 mL). The combined organic layers were washed with saturated brine (300 mL), dried over sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified over silica gel (400 g) eluting with heptanes to give compound (h) (50 g, 91% yield) as a light-yellow oil that slowly turned to an off-white solid on standing.

Reference： [1]Patent: WO2015/95188,2015,A1 .Location in patent: Paragraph 00187

44
[ 4688-76-0 ]
[ 57103-20-5 ]
3-(biphenyl-2-yl)-6-bromo-9-phenyl-9H-carbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
42%	In ethanol; toluene;	Example 3 Synthesis of 3-(biphenyl-2-yl)-6-bromo-9-phenyl-9H-carbazole A mixture of 40.1 g (100 mmol) of <strong>[57103-20-5]3,6-dibromo-9-phenyl-9H-carbazole</strong>, 21.8 g (110 mmol) of biphenyl-2-ylboronic acid, 2.31 g (2 mmol) of Pd(PPh3)4, 75 ml of 2M Na2CO3, 150 ml of EtOH and 300 ml toluene was degassed and placed under nitrogen, and then heated at 100° C. for 12 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The organic layer was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica to give product (19.9 g, 42.0 mmol, 42percent) as a white solid.

Reference： [1]Patent: US2015/214492,2015,A1 .Location in patent: Page/Page column

45
2-bromo-7-(5-methoxybiphenyl-2-yl)-9,9-dimethyl-9H-fluorene [ No CAS ]
[ 4688-76-0 ]
2-(biphenyl-2-yl)-7-(5-methoxybiphenyl-2-yl)-9,9-dimethyl-9H-fluorene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; at 110℃; for 8h;Inert atmosphere;	Synthesis of 2-(biphenyl-2-yl)-7-(5-methoxybiphenyl-2-yl)-9,9-dimethyl-9H-fluorene A mixture of 3.4 g (7.5 mmol) of 2-bromo-7-(5-methoxybiphenyl-2-yl)-9,9-dimethyl-9H-fluorene, 2 g (10 mmol) of biphenyl-2-ylboronic acid, 0.12 g (0.1 mmol) of tetrakis(triphenylphosphine)palladium, 15 ml of 2M Na2CO3, 20 ml of EtOH and 60 ml toluene was degassed and placed under nitrogen, and then heated at 110 C. for 8 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The reaction mixture was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was evaporated in vacuum. The residue was purified by column chromatography on silica(hexane-dichloromethane) afforded a white solid (2.7 g, 5.1 mmol, 68%).
	With tetrakis(triphenylphosphine) palladium(0); In ethanol; toluene;	Synthesis of 2-(biphenyl-2-yl)-7-(5-methoxybiphenyl-2-yl)-9,9-dimethyl-9H-fluorene A mixture of 3.4 g (7.5 mmol) of 2-bromo-7-(5-methoxybiphenyl-2-yl)-9,9-dimethyl-9H-fluorene, 2 g (10 mmol) of biphenyl-2-ylboronic acid, 0.12 g (0.1 mmol) of tetrakis(triphenylphosphine)palladium, 15 ml of 2M Na2CO3, 20 ml of EtOH and 60 ml toluene was degassed and placed under nitrogen, and then heated at 110 C. for 8 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The reaction mixture was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was evaporated in vacuum. The residue was purified by column chromatography on silica(hexane-dichloromethane) afforded a white solid (2.7 g, 5.1 mmol, 68%).

Reference： [1]Patent: US2016/204345,2016,A1 .Location in patent: Paragraph 0030-0031
[2]Patent: US9166177,2015,B2

46
[ 13697-89-7 ]
[ 4688-76-0 ]
2,6-difluoro-2'-phenyl-1,1'-biphenyl [ No CAS ]