[ CAS No. 99769-19-4 ] {[proInfo.proName]}

Name: 99769-19-4|3-(Methoxycarbonyl)phenylboronic acid|98%
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SKU: A225713
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Quality Control of [ 99769-19-4 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 99769-19-4 ]

SDS Specification

Alternatived Products of [ 99769-19-4 ]

Product Details of [ 99769-19-4 ]

CAS No. :	99769-19-4	MDL No. :	MFCD02093046
Formula :	C₈H₉BO₄	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	ALTLCJHSJMGSLT-UHFFFAOYSA-N
M.W :	179.97	Pubchem ID :	2734714
Synonyms :	3-(Methoxycarbonyl)phenylboronic acid	Chemical Name :	3-(Methoxycarbonyl)phenylboronic acid

Calculated chemistry of [ 99769-19-4 ]

Physicochemical Properties

Num. heavy atoms :	13
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.12
Num. rotatable bonds :	3
Num. H-bond acceptors :	4.0
Num. H-bond donors :	2.0
Molar Refractivity :	47.55
TPSA :	66.76 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) :	-6.91 cm/s

Lipophilicity

Log Po/w (iLOGP) :	0.0
Log Po/w (XLOGP3) :	0.68
Log Po/w (WLOGP) :	-0.85
Log Po/w (MLOGP) :	0.2
Log Po/w (SILICOS-IT) :	-0.87
Consensus Log Po/w :	-0.17

Druglikeness

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

Water Solubility

Log S (ESOL) :	-1.53
Solubility :	5.34 mg/ml ; 0.0297 mol/l
Class :	Very soluble
Log S (Ali) :	-1.66
Solubility :	3.95 mg/ml ; 0.0219 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-1.36
Solubility :	7.8 mg/ml ; 0.0434 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.85

Safety of [ 99769-19-4 ]

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 [ 99769-19-4 ]

* 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 [ 99769-19-4 ]
Downstream synthetic route of [ 99769-19-4 ]

[ 99769-19-4 ] Synthesis Path-Upstream 1~10

1
[ 99769-19-4 ]
[ 4467-07-6 ]

Reference： [1] Patent: WO2014/100734, 2014, A1,
[2] ACS Medicinal Chemistry Letters, 2016, vol. 7, # 2, p. 162 - 166

2
[ 99769-19-4 ]
[ 455-68-5 ]
[ 618-91-7 ]

Reference： [1] Organic Letters, 2013, vol. 15, # 19, p. 5134 - 5137

3
[ 99769-19-4 ]
[ 63555-50-0 ]

Reference： [1] Journal of the American Chemical Society, 2013, vol. 135, # 29, p. 10638 - 10641

4
[ 67-56-1 ]
[ 25487-66-5 ]
[ 99769-19-4 ]

Yield	Reaction Conditions	Operation in experiment
97.1%	at 55 - 65℃; Autoclave; Industrial scale	In a 20L reactor, 8.0 Kg of anhydrous methanol was added and carboxylbenzene acid 1.66 Kg (10 mol), stirring the reactor was heated to 55 , temperature 55 ~ 65 thionyl chloride was added dropwise to the kettle (1.78 Kg, 15 mol), dropwise after the reaction warmed to reflux for 2-3 hours.After completion of the reaction was confirmed (TLC: n-heptane: ethyl acetate = 2: 1), the reaction solution was cooled, the solvent evaporated under reduced pressure, after adding heptane, cooled -10 ~ 0 , stirred for 1 hour was filtered, Save 80 The solid was dried pressure until no impurities confirmation HNMR (HNMR: DMSO-d₆In 3.16ppm peak) to stop drying.Water was added after stirring at room temperature was filtered, dried at room temperature to give a white solid 1.75Kg, 97.1percent yield.

Reference： [1] Patent: CN106188117, 2016, A, . Location in patent: Paragraph 0015

5
[ 618-91-7 ]
[ 99769-19-4 ]

Reference： [1] Organic Letters, 2006, vol. 8, # 2, p. 305 - 307

6
[ 4518-10-9 ]
[ 13675-18-8 ]
[ 99769-19-4 ]

Reference： [1] Chemistry - A European Journal, 2014, vol. 20, # 22, p. 6608 - 6612

7
[ 618-89-3 ]
[ 99769-19-4 ]

Reference： [1] Organic Letters, 2012, vol. 14, # 18, p. 4814 - 4817,4

8
[ 2905-65-9 ]
[ 99769-19-4 ]

Reference： [1] Journal of the American Chemical Society, 2012, vol. 134, # 28, p. 11667 - 11673

9
[ 13675-18-8 ]
[ 99769-19-4 ]

Reference： [1] Chemistry - A European Journal, 2014, vol. 20, # 22, p. 6608 - 6612

10
[ 4518-10-9 ]
[ 99769-19-4 ]

Reference： [1] Chemistry - A European Journal, 2014, vol. 20, # 22, p. 6608 - 6612

[ 99769-19-4 ] Synthesis Path-Downstream 1~88

1
[ 104197-14-0 ]
[ 99769-19-4 ]
3',5'-difluoro-4'-methoxy-biphenyl-3-carboxylic acid methyl ester [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2004,vol. 47,p. 355 - 374

2
[ 26452-81-3 ]
[ 99769-19-4 ]
3-(6-methoxy-pyrimidin-4-yl)-benzoic acid methyl ester [ No CAS ]

Reference： [1]Tetrahedron Letters,2005,vol. 46,p. 3977 - 3979

3
[ 116632-23-6 ]
[ 98-88-4 ]
[ 99769-19-4 ]
3'-benzoylamino-5'-hydroxy-biphenyl-3-carboxylic acid methyl ester [ No CAS ]

Reference： [1]Tetrahedron Letters,2006,vol. 47,p. 4897 - 4901

4
[ 955368-90-8 ]
[ 99769-19-4 ]
[ 955369-40-1 ]

Yield	Reaction Conditions	Operation in experiment
	With pyridine;copper diacetate; In chloroform; at 20℃; for 72h;	1) Production of methyl 3-[2-allyl-6-(methylthio)-3-oxo-1,2-dihydro-3H-pyrazolo[3,4-d]pyrimidin-1-yl]benzoate 20 mL of pyridine was added to a chloroform solution of 7.5 g of <strong>[955368-90-8]2-allyl-6-(methylthio)-1,2-dihydro-3H-pyrazolo[3,4-d]pyrimidin-3-one</strong>, 6.1 g of copper(II) acetate and 10 g of [3-(methoxycarbonyl)]phenylboronic acid, and stirred at room temperature for 3 days. Aqueous 30% ammonia solution and saturated saline water were added to the reaction liquid in that order, and extracted with chloroform. The organic layer was washed with saturated saline water, then dried with anhydrous magnesium sulfate, and the solvent was evaporated away. The crude product was purified through silica gel column chromatography (hexane/ethyl acetate) to obtain 6.7 g of methyl 3-[2-allyl-6-(methylthio)-3-oxo-1,2-dihydro-3H-pyrazolo[3,4-d]pyrimidin-1-yl]benzoate as a yellow oily substance. 1H-NMR (400 MHz, CDCl3) delta: 8.92 (1H, s), 8.11-8.06 (2H, m), 7.65-7.59 (2H, m), 5.68 (1H, ddd, J=17.1, 10.2, 5.9 Hz), 5.13 (1H, dd, J=10.2, 1.0 Hz), 4.97 (1H, dd, J=17.1, 1.0 Hz), 4.45 (2H, d, J=5.9 Hz), 3.96 (3H, s), 2.51 (3H, s).
	With pyridine;copper diacetate; In chloroform; at 20℃; for 72h;	Production Example 11 Production of methyl 3-[2-allyl-6-(methylthio)-3-oxo-1,2-dihydro-3H-pyrazolo[3,4-d]pyrimidin-1-yl]benzoate Pyridine (20 mL) was added to a chloroform solution of <strong>[955368-90-8]2-allyl-6-(methylthio)-1,2-dihydro-3H-pyrazolo[3,4-d]pyrimidin-3-one</strong> (7.5 g), copper(II) acetate (6.1 g) and [3-(methoxycarbonyl)]phenylboronic acid (10 g), and stirred at room temperature for 3 days. Aqueous 30 % ammonia solution and saturated saline water were added to the reaction liquid in order, and extracted with chloroform. The organic layer was washed with saturated saline water, dried with anhydrous magnesium sulfate, and the solvent was evaporated away. The crude product was purified through silica gel column chromatography (hexane/ethyl acetate) to give methyl 3-[2-allyl-6-(methylthio)-3-oxo-1,2-dihydro-3H-pyrazolo[3,4-d]pyrimidin-1-yl]benzoate as a yellow oil (6.7 g). 1H-NMR (400 MHz, CDCl3) delta: 8.92 (1H, s), 8.11-8.06 (2H, m), 7.65-7.59 (2H, m), 5.68 (1H, ddt, J = 17.1, 10.2, 5.9 Hz), 5.13 (1H, dd, J = 10.2, 1.0 Hz), 4.97 (1H, dd, J = 17.1, 1.0 Hz), 4.45 (2H, d, J = 5.9 Hz), 3.96 (3H, s), 2.51 (3H, s).

Reference： [1]Patent: US2007/254892,2007,A1 .Location in patent: Page/Page column 38-39
[2]Patent: EP2213673,2010,A1 .Location in patent: Page/Page column 43; 44

5
[ 53087-13-1 ]
[ 99769-19-4 ]
[ 893736-53-3 ]

Yield	Reaction Conditions	Operation in experiment
60%	With barium dihydroxide;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 120℃; under 10343.2 Torr; for 0.116667h;Microwave;	A degassed mixture of 3-benzyloxy-phenyl bromide (28) (0.176 g, 0.67 mmol), 3- <n="55"/>methoxycarbonylphenylboronic acid (0.18 g, 1 mmol), barium hydroxide (0.25 g, 1.47 mmol), Pd(PPh3)4 (0.077 g, 0.067 mmol), DME (5 mL) and H2O (3 mL) was microwaved with vigorous stirring using a CEM-discover system (ram time: 2min, hold time: 5min, temperature: 12O0C, pressure: 200 psi, power: 250 W). The crude reaction mixture filtered through a plug of celite and concentrated in vacuo. The residue obtained was purified by flash column chromatography (25percent diethyl ether-hexane) to give the title compound (29) (0.118 g, 60percent yield) as a viscous liquid.1H NMR (500 MHz3 CDCl3) delta 8.27 (t, J = 1.5 Hz, IH), 8.20 (dd, J = 8.0 Hz, J = 1.5 Hz, IH)5 7.76 (dd, J = 8.0 Hz, J = 2.0 Hz, IH)5 7.50 (t, J = 8.0 Hz5 IH), 7.47 (d, J = 7.5 Hz, 2H), 7.42- 7.32 (m, 4H), 7.25-7.22 (m, 2H), 7.00 (dd, J = 8.2 Hz, J = 2.0 Hz, IH), 5.13 (s, 2H), 3.95 (s, 3H).
60%	With barium dihydroxide;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; at 120℃; under 10343.2 Torr; for 0.116667h;Microwave irradiation;	A degassed mixture of 3-benzyloxy-phenyl bromide (28) (0.176 g, 0.67 mmol), 3- methoxycarbonylphenylboronic acid (0.18 g, 1 mmol), barium hydroxide (0.25 g, 1.47 mmol), Pd(PPh3)4 (0.077 g, 0.067 mmol), DME (5 mL) and H2O (3 mL) was microwaved with vigorous stirring using a CEM-discover system (ram time: 2min, hold time: 5min, temperature: 120°C, pressure: 200 psi, power: 250 W). The crude reaction mixture filtered through a plug of celite and concentrated in vacuo. The residue obtained was purified by flash column chromatography (25percent diethyl ether-hexane) to give the title compound (29) (0.118 g, 60percent yield) as a viscous liquid.[0280] 29 was confirmed as follows: 1H NMR (500 MHz, CDCl3) delta 8.27 (t, J = 1.5 Hz, 1H), 8.20 (dd, J = 8.0 Hz, J = 1.5 Hz, 1H), 7.76 (dd, J = 8.0 Hz, J = 2.0 Hz, 1H), 7.50 (t, J = <n="95"/>8.0 Hz, 1H), 7.47 (d, J = 7.5 Hz, 2H), 7.42-7.32 (m, 4H), 7.25-7.22 (m, 2H), 7.00 (dd, J = 8.2 Hz, J = 2.0 Hz, 1H), 5.13 (s, 2H), 3.95 (s, 3H).
60%	With barium dihydroxide;Pd(PPh3)4; In 1,2-dimethoxyethane; water;	3'-Benzyloxy-biphenyl-3-carboxylic acid methyl ester (29) A degassed mixture of 3-benzyloxy-phenyl bromide (28) (0.176 g, 0.67 mmol), 3-methoxycarbonylphenylboronic acid (0.18 g, 1 mmol), barium hydroxide (0.25 g, 1.47 mmol), Pd(PPh3)4 (0.077 g, 0.067 mmol), DME (5 mL) and H2O (3 mL) was microwaved with vigorous stirring using a CEM-discover system (ram time: 2 min, hold time: 5 min, temperature: 120° C., pressure: 200 psi, power: 250 W). The crude reaction mixture filtered through a plug of celite and concentrated in vacuo. The residue obtained was purified by flash column chromatography (25percent diethyl ether-hexane) to give the title compound (29) (0.118 g, 60percent yield) as a viscous liquid. 1H NMR (500 MHz, CDCl3) delta 8.27 (t, J=1.5 Hz, 1H), 8.20 (dd, J=8.0 Hz, J=1.5 Hz, 1H), 7.76 (dd, J=8.0 Hz, J=2.0 Hz, 1H), 7.50 (t, J=8.0 Hz, 1H), 7.47 (d, J=7.5 Hz, 2H), 7.42-7.32 (m, 4H), 7.25-7.22 (m, 2H), 7.00 (dd, J=8.2 Hz, J=2.0 Hz, 1H), 5.13 (s, 2H), 3.95 (s, 3H).

Reference： [1]Patent: WO2008/13963,2008,A2 .Location in patent: Page/Page column 53-54
[2]Patent: WO2009/52319,2009,A1 .Location in patent: Page/Page column 93
[3]Patent: US2010/234379,2010,A1

6
[ 123172-90-7 ]
[ 99769-19-4 ]
[ 554451-45-5 ]

Yield	Reaction Conditions	Operation in experiment
75%	With potassium carbonate; lithium chloride;tetrakis(triphenylphosphine) palladium(0); In ethanol; toluene; at 20 - 80℃;	(27b) To a degassed solution of the triflate (1.49 g, 5.11 mmol) from (27a), 3-(methoxycarbonyl)phenylboronic acid (0.92 g, 1 eq), aq potassium carbonate (2.65 M, 3.8 mL, 2 eq) and lithium chloride (0.43 g, 2 eq) in ethanol (15 mL) and toluene (30 mL), was added tetrakis(triphenylphosphine)palladium (0.59 g, 0.1 eq) at rt. The mixture was stirred at 80 C. overnight. Water (50 mL) was added to the resulting black solution. The mixture was extracted with ethyl acetate (2×100 mL), washed with water, dried over MgSO4 and concentrated. The residue was purified by flash column chromatography (20% ethyl acetate-hexanes) to give the biaryl product (1.07 g, 75%).

Reference： [1]Patent: US2003/229084,2003,A1 .Location in patent: Page/Page column 38

7
[ 875781-36-5 ]
[ 99769-19-4 ]
3-[1-(2-methoxy-ethoxymethyl)-3-(2-methoxy-phenyl)-1H-pyrazolo[3,4-b]pyridin-5-yl]-benzoic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	With sodium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In water; acetonitrile; at 90℃; for 0.166667h;Microwave irradiation;	Step 1: Synthesis of 3-[l-(2-methoxy-ethoxymethyl)-3-(2-methosy-phenyl)-l^T-pyra2oIo[3,4-b]pyridm-5-yl]-bensoie acid methyl ester.[0261] A mixture of 5-bromo-l-(2-methoxy-ethoxymethyl)-3-(2-methoxy-phenyl)-17;/-pyrazolo[3,4-b]pyridine (535 mg, 1.36 mmol), 3-methoxycarbonylphenylboronic acid (258mg, 1.43 mmol) and l,r-bis(diphenylphosphino)ferrocenepalladium(ll)-dichloridedichlormethane adduct (50 mg, 68 umol) in acetonitrile (7 mL) and 2 M aqueous solution ofsodium carbonate (7 mL) was irradiated in a Personal Chemistry Optimizer at 90 C for 10minutes. The resulting mixture was distributed between ethyl acetate and water. Theaqueous phase was extracted twice with ethyl acetate and the combined organic phases werewashed with brine, dried over sodium sulfate, filtered and concentrated. The crude waspurified by flash silica gel chromatography using a gradient of ethyl acetate and hexanes toafford 3-[l-(2-methoxy-ethoxymethyl)-3-(2-methoxy-phenyl)-lJ7-pyrazolo[3,4-b]pyridin-5-yl]-benzoic acid methyl ester (612 mg, 1.36 mmol, 100 % yield) as a yellow oil. ^-NMR(500 MHz, 4-DMSO) £8.96 (d, 1H), 8.43 (d, 1H), 8.28 (t, 1H), 8.07 (td, 1H), 7.99 (td,1H), 7.67-7.69 (m, 2H), 7.51 (ddd, 1H), 7.25 (d, 1H), 7.12 (dt, 1H), 5.92 (s, 2H), 3.90 (s,3H), 3.87 (s, 3H), 3.73-3.75 (m, 2H), 3.43-3.45 (m, 2H), 3.21 (s, 3H). MS: m/z 372 [MH+].

Reference： [1]Patent: WO2006/15124,2006,A2 .Location in patent: Page/Page column 86

8
[ 875781-17-2 ]
[ 99769-19-4 ]
[ 875781-27-4 ]

Yield	Reaction Conditions	Operation in experiment
65%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 110℃; for 15h;Microwave irradiation;	Step 1: Synthesis of methyl 3-(lH-pyrazolo[3,4-b]pyridin-5-yl)benzoate.[0239] A mixture of 5-bromo-lH-pyrazolo[3,4-b]pyridine (2.00 g, 10.10 rntnol), 3-(methoxycarbonyl)phenylboronic acid (2.20 g, 12.12 mmol), sodium bicarbonate (2.2 g,6.00 mmol), and tetrakis(triphenylphosphine)palladium(0) (0.250 g, 0.202 mmol) indioxane/water (40 mL/10 mL) was stirred at 110 C for 15 hours. The mixture was thenpoured into ice water and extracted with ethyl acetate (3X). The organic layers werecombined, dried over sodium sulfate, filtered and concentrated to dryness. Silica gelchromatography of the crude product afforded methyl 3-(lH-pyrazolo[3,4-b]pyridin-5-yl)benzoate (8) (1.65 g, 65% yield) as yellow solids. MS: m/z 254.0 (M+H+).

Reference： [1]Patent: WO2006/15124,2006,A2 .Location in patent: Page/Page column 72

9
[ 887944-90-3 ]
[ 99769-19-4 ]
methyl 3-dibenzofuran-4-ylbiphenyl-3-yl-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%		Step 2. Methyl-3-dibenzofuran-4-ylbiphen-3-yl-carboxylate; A solution of 3-methoxycarbonyl-phenylboronic acid (0.62 g, 3.' mmol) in methanol (10 mL) was added to a stirred solution of 4- (3-bromophenyl) -dibenzofuran (1.0 g, 3.1 mmol) in toluene (40 EPO <DP n="124"/>itiL) . tetrakis- (Triphenylphosphine)palladium(0) (180 mg, 5 mol%) and 2N sodium carbonate (3.1 mL, 6.2 mmol) were added and the reaction was heated to 9O0C (oil bath temp.) for 2-3 hrs until complete (TLC control) . The reaction mixture was cooled to room temperature and partitioned between water and ethyl acetate. The phases were separated, the aqueous phase being further extracted with ethyl acetate (2 x 20 mL) . The combined extract was washed with 0.5 N hydrochloric acid, water and brine and then dried over anhydrous MgSO4, filtered and concentrated in vacuo. Purification of the product by flash column chromatography, using 10-20% ethyl acetate in hexane as eluent, afforded the title compound; methyl-3-dibenzofuran-4- ylbiphen-3-yl-carboxylate has a white solid (1.10 g, 94%) .

Reference： [1]Patent: WO2006/55625,2006,A2 .Location in patent: Page/Page column 122-123

10
[ 861673-68-9 ]
[ 99769-19-4 ]
methyl 3-(2-(2-tert-butylphenoxy)pyridin-3-ylamino)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With pyridine; copper diacetate; triethylamine; In 1,2-dichloro-ethane; at 20℃; for 16h;Molecular sieve;	Example 1 methyl 3-(2-(2-tert-butylphenoxy)pyridin-3-ylamino)benzoate To a solution of Intermediate 1 (100 mg, 0.414 mmol) in 1,2-dichloroethane (4 mL) in a 25 mL scintillation vial under air was added 3-(methoxycarbonyl)phenylboronic acid (148 mg, 0.818 mmol), triethylamine (120 muL), pyridine (120 muL), powdered 4 A sieves (150 mg) and lastly Cu(OAc)2 (51 mg, 0.28 mmol). The reaction was stirred overnight (~16 h) at rt. The reaction was filtered through a 40 mum filter and solvent removed. Purification by flash chromatography (40 g ISCO silica gel cartridge, 0-15% Ether/Hexane) provided Example 1 (93 mg). (M+H)+=377.34. 1H NMR (400 MHz, CD3OD) delta ppm 1.31 (s, 9H), 3.87 (s, 3H), 6.92 (dd, J=8.14, 1.76 Hz, 1H), 7.01 (dd, J=7.92, 4.84 Hz, 1H), 7.11 (td, J=7.92, 1.32 Hz, 1H), 7.19 (m, 1H), 7.34 (m, 2H), 7.42 (dd, J=7.92, 1.76 Hz, 1H), 7.54 (m, 1H), 7.61 (dd, J=4.84, 1.32 Hz, 1H), 7.66 (dd, J=7.92, 1.76 Hz, 1H), 7.73 (dd, J=2.16, 1.76 Hz, 1H); 13C NMR (400 MHz, CD3OD) delta ppm 30.9, 35.5, 52.6, 119.6, 120.1, 123.0, 123.8, 124.2, 125.6, 126.9, 128.0, 128.3, 130.4, 130.5, 132.3, 139.0, 142.7, 144.9, 154.1, 156.1, 168.7.

Reference： [1]Patent: US2006/293522,2006,A1 .Location in patent: Page/Page column 19

11
[ 905590-33-2 ]
aqueous potassium carbonate [ No CAS ]
[ 99769-19-4 ]
[ 247940-06-3 ]
3-(2-[4-(3,4-diethoxyphenyl)-4-oxobutanoyl]amino}-6-phenylpyridin-4-yl)benzoic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	tris-(dibenzylideneacetone)dipalladium(0);	Example 139 methyl 3-(2-[4-(3,4-diethoxyphenyl)-4-oxobutanoyl]amino}-6-phenylpyridin-4-yl)benzoate Using N-(4-chloro-6-phenylpyridin-2-yl)-4-(3,4-diethoxyphenyl)-4-oxobutanamide obtained in Example 43-(3) (22.6 mg), tris(dibenzylideneacetone)dipalladium (1.1 mg), biphenyl-2-yl(dicyclohexyl)phosphine (1.8 mg), 1N aqueous potassium carbonate solution (0.1 mL) and [3-(methoxycarbonyl)phenyl]boronic acid (22.5 mg) as starting materials and in the same manner as in Example 119, methyl 3-(2-[4-(3,4-diethoxyphenyl)-4-oxobutanoyl]amino}-6-phenylpyridin-4-yl)benzoate (13.9 mg) was obtained. HPLC (220 nm) purity 97% (retention time 2.14 min) MS (ESI+, m/e) 553 (M+H)

Reference： [1]Patent: EP1845081,2007,A1

12
[ 905590-58-1 ]
aqueous potassium carbonate [ No CAS ]
[ 99769-19-4 ]
[ 247940-06-3 ]
3-(2-[4-(2,3-dihydro-1-benzofuran-5-yl)-4-oxobutanoyl]amino}-6-phenylpyridin-4-yl)benzoic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	tris-(dibenzylideneacetone)dipalladium(0);	Example 170 methyl 3-(2-[4-(2,3-dihydro-1-benzofuran-5-yl)-4-oxobutanoyl]amino}-6-phenylpyridin-4-yl)benzoate Using N-(4-chloro-6-phenylpyridin-2-yl)-4-(2,3-dihydro-1-benzofuran-5-yl)-4-oxobutanamide obtained in Example 114-(1) (20.3 mg), tris(dibenzylideneacetone)dipalladium (1.1 mg), biphenyl-2-yl(dicyclohexyl)phosphine (1.8 mg), 1N aqueous potassium carbonate solution (0.1 mL) and [3-(methoxycarbonyl)phenyl]boronic acid (22.5 mg) as starting materials and in the same manner as in Example 119, methyl 3-(2-[4-(2,3-dihydro-1-benzofuran-5-yl)-4-oxobutanoyl]amino}-6-phenylpyridin-4-yl)benzoate (13.6 mg) was obtained. HPLC (220 nm) purity 99% (retention time 2.09 min) MS (ESI+, m/e) 507 (M+H)

Reference： [1]Patent: EP1845081,2007,A1

13
[ 1033593-89-3 ]
[ 99769-19-4 ]
[ 1033593-87-1 ]

Yield	Reaction Conditions	Operation in experiment
51%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 100℃; for 24h;	The product (100 mg, 0.267 mmol) and 3-methoxycarbonyl- phenylboronic acid (58 mg, 0.33 mmol) was dissolved in toluene (1.5 ml)/ethanol (0.5 ml). 1 ml of 2M aqueous sodium carbonate and tetrakistriphenylphosphine palladium (15 mg, 0.013 mmol) was added thereto, and refluxed at 100 C for 24 hours. The resulting mixture was diluted with water (10 ml), and extracted three times with dichloromethane. Then, the dichloromethane was removed therefrom, and the resulting residue was purified by column chromatography (dichloromethane :methanol=20: l) to obtain the title compound as colorless solid (65 mg, 51%). m.p 86-88 C ; MS(ESI)[M+H+]475;1H NMR (250 MHz, CDCl3) delta 9.03-8.97(1H, m), 8.61-8.53(1H, m), 8.16(1H, d, J=7.5 Hz), 7.56-7.50(1H, m), 7.27-7.22(4H, m), 5.41-5.3O(1H, m), 5.12-5.O6(1H, m), 4.68-4.53(1H, m), 4.15(4H, bs), 3.96(3H, s), 3.67(3H, bs), 3.18-3.O9(1H, m), 2.93-2.86(1H, m), 2.71(4H, s), 2.51(3H, s).

Reference： [1]Patent: WO2008/72850,2008,A1 .Location in patent: Page/Page column 32

14
[ 1899-24-7 ]
[ 99769-19-4 ]
methyl 3-(5-formylfuran-2-yl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	With Pd(N,N-dimethyl-beta-alaninate)2; sodium carbonate; In ethanol; water; at 120℃; for 0.166667h;Microwave irradiation; Sealed tube;	General procedure: To a solution of the appropriate bromo-substituted heterocyclic aldehydes 17a (1.0 mmol) in EtOH/H2O 5:3 (tot 12 mL) in a 35 mL CEM microwave vessel, the correspondent boronic acids 18c-d (1.2 mmol), Na2CO3 2M (2.0 mmol) and Pd(N,N-Dimethyl beta-alaninate)2 (5 mol%) were added. The vessel was capped and placed in a microwave reactor and the reaction carried out with the following method in dynamic mode: 120 C, 10 min, 50W, with high stirring. After completion the vessel was allowed to cool to room temperature and the mixture was extracted with EtOAc (3 X 10 mL). The organic phase was collected, dried over anhydrous Na2SO4, and the solvent evaporated under vacuum. The crude product (containing a small portion of the ethyl ester as a transesterification product) was then purified via silica gel column chromatography (petroleum ether/EtOAc elution gradient from a 90/10 ratio to a 80/20 ratio) to obtain the pure compounds (yield 40-60%) (Scheme 1).

Reference： [1]Journal of the American Chemical Society,2015,vol. 137,p. 10464 - 10467
[2]European Journal of Medicinal Chemistry,2015,vol. 101,p. 63 - 70
[3]Bioorganic and Medicinal Chemistry Letters,2008,vol. 18,p. 4022 - 4026

15
[ 854771-08-7 ]
[ 99769-19-4 ]
[ 1127737-41-0 ]

Yield	Reaction Conditions	Operation in experiment
70%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; toluene; at 90℃; for 4h;	Step 1: 3-Benzyl-4-(3-bromophenyl)-8-(trifluoromethyl)quinoline (300 mg, 0.68 mmol) was taken into toluene/EtOH (3 mL/0.5 mL). Then 3-(methoxycarbonyl)phenylboronic acid (0.183 mg, 1.0 mmol) was added followed by 2 M Na2CO3 (1.7 mL, 3.4 mmol) and finally Pd(PPh3)4 (39 mg, 0.034 mmol). The reaction was heated at 90 C. for 4 hours. The solvent was removed and the resulting material was purified via column chromatography using 5% ethyl acetate in hexane to elute out (0.235 g, 70%) of methyl 3'-[3-benzyl-8-(trifluoromethyl)quinolin-4-yl]biphenyl-3-carboxylate; MS (ES) m/z 497.9.

Reference： [1]Patent: US2009/69373,2009,A1 .Location in patent: Page/Page column 31-32

16
[ 1007206-24-7 ]
[ 99769-19-4 ]
[ 1007213-69-5 ]

Yield	Reaction Conditions	Operation in experiment
90%	dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate; In N,N-dimethyl-formamide; at 100℃; for 2h;	Example 1-G-01 3-(2-Morpholin-4-yl-7-pyridin-3-yl-6,7-dihydro-5H-pyrrolo[2,3-d]pyrimidin-4-yl)-benzoic acid methyl ester (G-01) [Show Image] 4-Chloro-2-morpholin-4-yl-7-pyridin-3-yl-6,7-dihydro-5H-pyrrolo[2,3-d]pyrimidine (317 mg, 1.00 mmol), palladium acetate (11 mg, 5 mol%), S-Phos (41 mg, 10 mol%) and 3-methoxycarbonylphenylboronic acid (637 mg) were dissolved in dimethylformamide (10 ml). Then, argon substitution was carried out three times under ultrasonic irradiation in reduced pressure. The reaction mixture was stirred at 100C for 2 hours, and the reaction mixture was allowed to cool to room temperature, and then poured onto water (100 ml). The reaction mixture was extracted twice with ethyl acetate/tetrahydrofuran (4/1,100 ml), and the combined organic layers were washed with brine, followed by drying over sodium sulfate. After the drying agent was filtered off, the filtrate was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (dichloromethane/methanol=100/0 to 50/1), to obtain a colorless solid (374 mg, 90%). 1H-NMR (270 MHz, CDCl3) delta (ppm): 9.12 (1H, d, J=2.7Hz), 8.54 (1H, d, J=1.6Hz), 8.31 (1H, dd, J=4.6,1.6Hz), 8.05-8.18 (3H, m), 7.55 (1H, t, J=7.6Hz), 7.32 (1H, dd, J=8.4, 4,6Hz), 4.11 (2H, t, J=8.4Hz), 3.96 (3H, s), 3.77-3.89 (8H, m), 3.40 (2H, t, J=8.4Hz). ESI (LC-MS positive mode) m/z 418 [(M+H)+].

Reference： [1]Patent: EP2050749,2009,A1 .Location in patent: Page/Page column 415

17
[ 2941-58-4 ]
[ 99769-19-4 ]
[ 1097776-75-4 ]

Yield	Reaction Conditions	Operation in experiment
53%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; at 80℃; for 1h;	To a slurry of 2-bromo-6-(methyloxy)-l,3-benzothiazole (0.57 g, 2.34 mmol), tetrakis(triphenylphosphine)palladium(0) (0.108 g, 0.093 mmol), ethylene glycol dimethyl ether (14 mL) and 2 N sodium carbonate (11 mL, 22 mmol) was added {3- [(methyloxy)carbonyl]phenyl}boronic acid (0.5 g, 2.80 mmol) and the reaction mixture was heated at 80 0C for 1 h. The reaction mixture was cooled to room temperature then diluted with ethyl acetate, followed by water. The ethyl acetate layer was separated, washed with brine, dried over magnesium sulfate, filtered, and concentrated. The crude material was purified by flash chromatography over silica using a hexanes:ethyl acetate gradient of 0 to 30% ethyl acetate to afford 0.37 g (53%) of methyl 3-[6-(methyloxy)-l,3-benzothiazol-2-yl]benzoate. 1H NMR (400 MHz, DMSO-J6): delta 8.57 (t, J = 2 Hz, IH), 8.27 (d, J = 8 Hz, IH), 8.08 (d, J = 8 Hz, IH), 7.98 (d, J = 9 Hz, IH), 7.74 (d, J = 3 Hz, IH), 7.70 (t, J = 8 Hz, IH), 7.15 (dd, J = 9, 3 Hz, IH), 3.90 (s, 3H), 3.84 (s, 3H).

Reference： [1]Patent: WO2009/5998,2009,A1 .Location in patent: Page/Page column 118
[2]Bioorganic and Medicinal Chemistry Letters,2009,vol. 19,p. 4733 - 4739

18
[ 5111-65-9 ]
[ 99769-19-4 ]
[ 1097777-54-2 ]

Yield	Reaction Conditions	Operation in experiment
36%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In toluene; at 20℃;Reflux;	2-Bromo-6-methoxynaphthalene (0.824 g, 3.48 mmol), (3- methoxycarbonylphenyl)boronic acid (0.57 g, 3.17 mmol), tetrakistriphenylphosphine palladium(O) (0.217g, 0.188 mmol), sodium carbonate (2 M) (6.4 mL, 12.8 mmol), and toluene (20 mL) were combined in a round bottom flask and the stirred reaction mixture was heated at reflux for 3 h under a nitrogen atmosphere. The reaction mixture was allowed to stand at room temperature overnight. To the reaction mixture was added <strong>[99769-19-4](3-methoxycarbonylphenyl)boronic acid</strong> (0.496 g, 2.7 mmol) and the reaction mixture was heated at reflux for 2 h under a nitrogen atmosphere. The reaction mixture was allowed to cool at room temperature and partitioned between water and ethyl acetate. The organic phase was separated, dried over magnesium sulfate, filtered, and the filtrate was concentrated to give the crude product. The crude product was purified by flash chromatography over silica with a hexanes: ethyl acetate gradient (100:0 to 80:20) to give 0.335 g (36% ) of methyl 3-[6-(methyloxy)-2- naphthalenyl]benzoate as a white solid. 1H NMR (400 MHz, CDCl3): delta 8.38 (s, IH), 8.05 (m, 2H), 7.89 (d, J = 8 Hz, IH), 7.82 (t, J = 8 Hz, 2H), 7.73 (dd, J = 8, 2 Hz, IH), 7.54 (t, J = 8 Hz, IH), 7.19 (m, 2H), 3.96 (s, 3H), 3.94 (s, 3H). ESI-LCMS m/z 293 (M+H)+.

Reference： [1]Patent: WO2009/5998,2009,A1 .Location in patent: Page/Page column 185-186
[2]Bioorganic and Medicinal Chemistry Letters,2009,vol. 19,p. 4733 - 4739

19
[ 135653-94-0 ]
[ 99769-19-4 ]
[ 1097777-34-8 ]

Yield	Reaction Conditions	Operation in experiment
88%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; at 80℃; for 1h;	To a slurry of 7-(methyloxy)-2-naphthalenyl trifluoromethanesulfonate (2.7 g, 8.82 mmol), tetrakis(triphenylphosphine)palladium(0) (0.41 g, 0.353 mmol), ethylene glycol dimethyl ether (47.5 mL) and 2 N sodium carbonate (43 mL, 86 mmol) was added {3-[(methyloxy)carbonyl]phenyl}boronic acid (1.9 g, 10.58 mmol) and the reaction mixture was heated at 80 0C for 1 h. The reaction mixture was cooled to room temperature and diluted with water, followed by ethyl acetate. The organic layer <n="169"/>was washed with water followed by brine, dried over magnesium sulfate, filtered, and concentrated. The crude material was purified by flash chromatography over silica using a hexanes:ethyl acetate gradient of 0 to 30% ethyl acetate to afford 2.25 g (88%) of methyl 3-[7-(methyloxy)-2-naphthalenyl]benzoate. 1H NMR (400 MHz, DMSO- d6): delta 8.31 (t, J = 2 Hz, IH), 8.17 (d, J = 2 Hz, IH), 8.07 (m, IH), 7.97 (m, IH), 7.94 (d, J = 9 Hz, IH), 7.85 (d, J = 9 Hz, IH), 7.67 (m, 2H), 7.45 (d, J = 2 Hz, IH), 7.17 (dd, J = 9, 3 Hz, IH), 3.89 (s, 3H), 3.87 (s, 3H)

Reference： [1]Patent: WO2009/5998,2009,A1 .Location in patent: Page/Page column 167-168

20
[ 15864-32-1 ]
[ 99769-19-4 ]
[ 1097777-51-9 ]

Yield	Reaction Conditions	Operation in experiment
26%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; at 20 - 85℃;	2-Amino-6-bromobenzothiazole (1.75 g, 7.6 mmol), (3- methoxycarbonylphenyl)boronic acid (1.8 g, 10 mmol), sodium carbonate (2 M) (7 mL, 14 mmol), tetrakis(triphenylphosphine)palladium(0) (0.48 g, 0.42 mmol), and 1 ,2-dimethoxyethane (75 mL) were combined and the stirred reaction mixture was heated at 85 0C for 4 h under a nitrogen atmosphere. The reaction mixture was allowed to stand at room temperature overnight. To the reaction mixture was added tetrakis(triphenylphosphine)palladium(0) (0.10 g, 0.087 mmol) and the reaction mixture was heated at 85 0C for 3 h. The reaction mixture was allowed to stand at room temperature for three days. To the reaction mixture was added tetrakis(triphenylphosphine)palladium(0) (0.146 g, 0.126 mmol) and sodium carbonate (2 M) (20 mL, 40 mmol). The reaction mixture was heated at 85 0C for 3 h under a nitrogen atmosphere. The reaction mixture was allowed to cool at room temperature. The reaction mixture was partitioned between water and ethyl acetate. The aqueous phase was separated and extracted with ethyl acetate. The organic extracts were combined, washed with saturated sodium chloride, dried over magnesium sulfate, filtered, and the filtrate was concentrated to give a red-orange liquid which partially solidified upon standing. Ethyl acetate was added to the crude product and the mixture was heated. The solvent was removed in vacuo. To the crude product was added dichloromethane, methanol, and ethyl acetate. The suspension was filtered to give 0.179 g of methyl 3-(2-amino-l,3-benzothiazol-6- <n="184"/>yl)benzoate as an off-white solid. The filtrate was adsorbed onto silica and purified by flash chromatography with hexanes, followed by hexanes: ethyl acetate (1 :1) and finally ethyl acetate to give 0.377 g of methyl 3-(2-amino-l,3-benzothiazol-6- yl)benzoate as a tan solid for a total yield of 0.556 g (26%). 1H NMR (400 MHz, DMSO-J6): delta 8.17 (s, IH), 8.03 (d, J = 2 Hz, IH), 7.92 (d, J = 8 Hz, IH), 7.88 (d, J = 8 Hz, IH), 7.52-7.59 (m, 4H), 7.39 (d, J = 8 Hz, IH), 3.86 (s, 3H). ESI-LCMS m/z 285 (M+H)+.

Reference： [1]Patent: WO2009/5998,2009,A1 .Location in patent: Page/Page column 182-183
[2]Bioorganic and Medicinal Chemistry Letters,2009,vol. 19,p. 4733 - 4739

21
[ 3199-50-6 ]
[ 99769-19-4 ]
[ 1202918-49-7 ]

Yield	Reaction Conditions	Operation in experiment
61%	With caesium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; water; at 105℃; for 3h;Inert atmosphere;	Example 28 Synthesis of methyl 3-(5-acetylfuran-2-yl)benzoate To a solution of <strong>[3199-50-6]1-(5-bromofuran-2-yl)ethanone</strong> (2 g, 10.58 mmol) and cesium carbonate (10.35 g, 31.74 mmol in water/dioxane (5%, 20 mL), flushed with nitrogen for 15 minutes, was added 3-methoxycarbonylphenyl boronic acid (2.09 g, 11.64 mmol), followed by catalyst PdCl2(dppf) (379 mg, 0.519 mmol). The solution was heated to reflux (105 C.) under nitrogen, for 3 hours. Water (100 mL) was added to the mixture after cooling down to rt. Filtration gave 2.56 g of a black crude material. Purification via silica column chromatography eluding with dichloromethane gave methyl 3-(5-acetylfuran-2-yl)benzoate (1.58 g, 6.19 mmol, 61% yield) as a yellow solid. LCMS (ES): m/z 245 [M+1]+.
49%	With potassium phosphate; palladium diacetate; CyJohnPhos; In toluene; at 90℃;Inert atmosphere;	A mixture of <strong>[3199-50-6]1-(5-bromofuran-2-yl)ethanone</strong> (24, 1.57g, 8.3mmol), 3-(methoxycarbonyl)phenylboronic acid (23c, 1.71g, 9.5mmol), (2-biphenyl)dicyclohexylphosphine (0.29g, 0.83mmol) and K3PO4 (7.10g, 33.5mmol) was suspened in toluene (36mL) under argon for 20min. Then Pd(OAc)2 (114.5mg, 0.51mmol) was added, and the resulting suspension was heated to 90C and stirred under argon overnight in a sealed tube. After cooling down, the solvent was evaporated. The crude residue was further purified by silica gel column chromatography, eluting with hexane-ethyl acetate 8:2, to provide the product as light yellow solid (1.00g, 49%): mp 117-118C. 1H NMR (300MHz, CDCl3) delta 8.38 (t, J=1.5Hz, 1H), 8.01-7.93 (m, 2H), 7.49 (t, J=7.8Hz, 1H), 7.25 (d, J=3.6Hz, 1H), 6.84 (d, J=3.6Hz, 1H), 3.93 (s, 3H), 2.52 (s, 3H); 13C NMR (75MHz, CDCl3) delta 186.3, 166.4, 156.4, 152.1, 130.9, 129.9, 129.6, 129.0, 128.9, 125.9, 119.3, 108.2, 52.3, 26.0.

Reference： [1]ACS Medicinal Chemistry Letters,2012,vol. 3,p. 135 - 139
[2]Patent: US2010/41635,2010,A1 .Location in patent: Page/Page column 111
[3]Bioorganic and Medicinal Chemistry,2014,vol. 22,p. 406 - 418

22
[ 109-04-6 ]
[ 99769-19-4 ]
[ 98061-20-2 ]

Yield	Reaction Conditions	Operation in experiment
74%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; In 1,4-dioxane; water; at 120℃; for 0.5h;Microwave irradiation;	[00335] A solution <strong>[99769-19-4](3-(methoxycarbonyl)phenyl)boronic acid</strong> (500 mg, 2.78 mmol), 2- bromopyridine (399 mg, 2.53 mmol), K2CO3 (1.0 g, 7.6 mmol) and Pd(dppf)Cl2 (20 mg) in a mixture of dioxane (10 mL) and water (2.5 mL) was heated under microwave conditions at 120 C for 0.5 h. The reaction mixture was filtered, concentrated, and the crude product was purified by column chromatography eluting with petroleum ether/ethyl acetate (5: 1). (400 mg, yield 74%) MS (ESI+) e/z: 214.1 [M+l]+.
70%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In methanol; water; toluene; at 80℃; for 24h;Inert atmosphere;	General procedure: Method A: The preparation of 2-Bromopyridines with arylboronic acids was according to literature procedures.[1] To a 50-mL fire-dried flask was charged with 2-Bromopyridines (5 mmol, 1.0 eq ), arylboronic acid (5.5 mmol, 1.5 eq), Na2CO3 (1.06 g, 10.0 mmol, 2.0 eq), Pd(PPh3)4 (173.4 mg, 0.03 mmol, 3.0 mol%), distilled water (2.5 mL), toluene (10.0 mL) and methanol (2.0 mL). The mixture was degassed through a freeze-thaw-pump thread for three times. The reaction was stirred at 80 C for 24 hours. To the reaction mixture was added brine (15 mL) and ethyl acetate (15 mL). The phase was separated and the aqueous phase was extracted with ethyl acetate (4 × 15 mL). The combined organic phase was dried over Na2SO4 and concentrated under vacuum. The product was isolated by flash-column chromatography on silica gel (300-400 mesh).

Reference： [1]Patent: WO2014/100734,2014,A1 .Location in patent: Paragraph 00335
[2]Tetrahedron,2019,vol. 75,p. 2547 - 2552
[3]Journal of Medicinal Chemistry,2018,vol. 61,p. 5679 - 5691
[4]Journal of the American Chemical Society,2010,vol. 132,p. 922 - 923
[5]ACS Medicinal Chemistry Letters,2016,vol. 7,p. 162 - 166
[6]Organic Letters,2019,vol. 21,p. 3735 - 3740

23
[ 99769-19-4 ]
[ 618-51-9 ]
[ 893736-81-7 ]

Yield	Reaction Conditions	Operation in experiment
83%		Step 1: Preparation of 3'-(methoxycarbonyl)biphenyl-3-carboxylic acid <n="92"/>[00147] 3-Iodobenzoic acid (1.0 g, 4.03 mmol, 1 equiv.), 3- (methoxycarbonyl)phenylboronic acid (0.73 g, 4.03 mmol, 1 equiv.), and Pd(OAc)2 (27 mg, 0.12 mmol, 0.03 equiv.) were mixed in DMF (10 mL) at RT with stirring, followed by the addition of 1.5M cesium carbonate (8.06 mL, 1.16 mmol, 3 equiv.). The mixture was heated at 40 0C for 4 hours. At the conclusion of this period, the reaction was worked up by adding water and adjusting the pH to 3 with IN HCl. The aqueous mixture was extracted (3X) with EtOAc/THF. The organic layers were rinsed (3X) with water. The organic layer was dried over sodium sulfate and concentrated to give an off-white solid. The solid was stirred in hexanes (10 mL), filtered and dried under high vacuum to give 3 '-(methoxycarbonyl)biphenyl-3- carboxylic acid (860 mg, 3.36 mmol, 83% yield) as a white solid. MS (ESI+) = 257.23 (M+H)+

Reference： [1]Patent: WO2009/15166,2009,A1 .Location in patent: Page/Page column 90-91

24
[ 6303-46-4 ]
[ 99769-19-4 ]
[ 1228298-37-0 ]

Reference： [1]Journal of the American Chemical Society,2010,vol. 132,p. 7043 - 7048

25
[ 557-21-1 ]
[ 99769-19-4 ]
[ 13531-48-1 ]

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

26
[ 1283116-62-0 ]
[ 99769-19-4 ]
[ 1283116-84-6 ]

Yield	Reaction Conditions	Operation in experiment
61%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 170℃; for 0.283333h;Inert atmosphere; Sealed vessel; Microwave irradiation;	General procedure: A mixture of arylbromide (142 mg, 0.2 mmol), boronic acid (36 mg, 0.22 mmol), K2CO3 (69 mg, 0.5 mmol) and Pd(PPh3)4 (34 mg, 0.03 mmol) was suspended in DMF (0.1 M) in a sealed tube vessel and irradiated in a Biotage Initiator microwave reactor (17 min, 170 C). After cooling to rt, the reaction was diluted with water and repeatedly extracted with CH2Cl2. The combined organic extracts were washed with brine, dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure.

Reference： [1]Bioorganic and Medicinal Chemistry,2011,vol. 19,p. 1823 - 1838

27
[ 1285505-77-2 ]
[ 99769-19-4 ]
[ 1285504-30-4 ]

Yield	Reaction Conditions	Operation in experiment
31%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 90℃;	Example 16Synthesis of (E)-2'-(3-guanidino-2-methyl-3-oxo-propenyl)-biphenyl-3-carboxylic acid methyl ester<Step 1>Intermediate 1 (20 mg, 0.05 mmol) and 3-methoxycarbonylphenylboronic acid (10 mg, 0.06 mmol) were dissolved in a mixed solution of dioxane and water (v/v=3/1, 3 mL). Pd(PPh3)4 (3.00 mg, 2.60 mumol) and Na2CO3 (21.0 mg, 0.2 mmol) were added to the solution and then stirred at 90 C. overnight. After cooling it to room temperature, the solvent was eliminated in vacuo and then purified by reversed phase HPLC (0.1% TFA in water/CH3CN) to obtain the compound of Example 16 (3.3 mg, 31%).MS: 338

Reference： [1]Patent: US2011/82109,2011,A1 .Location in patent: Page/Page column 17

28
[ 52415-29-9 ]
[ 99769-19-4 ]
[ 1202502-26-8 ]

Yield	Reaction Conditions	Operation in experiment
50%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 90℃; for 5h;Inert atmosphere;	Reference Example 1 methyl 3-(1H-indol-6-yl)benzoate A mixture of 6-bromo-1H-indole (1.00 g, 5.10 mmol), <strong>[99769-19-4][3-(methoxycarbonyl)phenyl]boronic acid</strong> (1.10 g, 6.12 mmol) and tetrakis(triphenylphosphine)palladium(0) (295 mg, 0.255 mmol) in 2 N aqueous sodium carbonate solution (20 mL)-1,2-dimethoxyethane (30 mL) was reacted under a nitrogen atmosphere at 90C for 5 hr. To the reaction mixture was added saturated brine and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give the title compound (638 mg, yield 50%) as crystals. 1H-NMR (CDCl3) delta : 3.95 (3H, s), 6.58 (1H, t, J = 2.1 Hz), 7.25 (1H, t, J = 2.8 Hz), 7.41 (1H, dd, J = 8.3, 1.7 Hz), 7.49 (1H, t, J = 7.8 Hz), 7.62 (1H, s), 7.71 (1H, d, J = 8.3 Hz), 7.79 - 7.87 (1H, m), 7.95 - 8.02 (1H, m), 8.30 (1H, brs), 8.34 (1H, t, J = 1.8 Hz).

Reference： [1]Patent: EP2298731,2011,A1 .Location in patent: Page/Page column 49

29
[ 1256162-94-3 ]
[ 99769-19-4 ]
[ 1256163-00-4 ]

Yield	Reaction Conditions	Operation in experiment
70%	With caesium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; water; at 105℃;Inert atmosphere;	To 5-chloropyrazolo[l,5-a]pyrimidine-3-carbaldehyde (115mg, 0.64mmol) in dioxane/water (2850 mu, /150 mu) was added 3-(methoxycarbonyl)phenylboronic acid (171 mg, 0.95 mmol), and cesium carbonate (623 mg, 1.91 mmol). The mixture was degassed under nitrogen for 10 minutes and then PdCl2dppf (23 mg, 0.03 mmol) was added. The mixture was heated at 105 C overnight. Water was added and the resulting solid was isolated by filtration. The solid was then dissolved in dichloromethane and washed with water, dried over Na2S04 and passed through a plug of silica. The resulting solution was concentrated under vacuum to yield 125 mg of 3-(3-formylpyrazolo[l,5-a]pyrimidin-5- yl)benzoate as a yellow solid (70% yield). LCMS (M+ 1=282)

Reference： [1]Patent: WO2011/31979,2011,A1 .Location in patent: Page/Page column 79

30
[ 1193-18-6 ]
[ 99769-19-4 ]
[ 1289577-21-4 ]

Yield	Reaction Conditions	Operation in experiment
91%	With palladium(II) trifluoroacetate; 2-[(S)-4,5-dihydro-4-tert-butyl-1,3-oxazol-2-yl]pyridine; In 1,2-dichloro-ethane;Heating;	General procedure: Synthesized according to the general procedure and purified by flash chromatography (CH2Cl2/EtOAc 100:0 to 98:2) to afford a white solid (91% yield). 1H NMR (500 MHz, CDCl3) delta 8.03 (dd, J=1.5, 2.0 Hz, 1H), 7.88 (dd, J=1.5, 9.0 Hz, 1H), 7.51 (dd, J=2.0, 9.0 Hz, 1H), 7.39 (dd, J=9.0 Hz, 1H), 3.91 (s, 3H), 2.88 (d, J=14.0 Hz, 1H), 2.47 (d, J=14.0 Hz, 1H), 2.37-2.28 (m, 2H), 2.24-2.19 (m, 1H), 1.98-1.86 (m, 2H), 1.73-1.65 (m, 1H), 1.33 (s, 3H); 13C NMR (125 MHz, CDCl3) delta 210.9, 167.1, 147.9, 130.4, 130.2, 128.6, 127.5, 126.7, 53.0, 52.1, 42.8, 40.7, 37.7, 29.3, 22.0; IR (Neat Film, NaCl) 2952, 2878, 1720, 1604, 1582, 1438, 1350, 1310, 1273, 1243, 1209, 1194, 1120, 1085 cm-1; HRMS (MultiMode ESI/APCI) m/z calcd for C15H19O3 [M+H]+: 247.1329, found 247.1334; [alpha]D25 -58.9 (c 1.39, CHCl3, 95% ee). A screw-top 1 dram vial was charged with a stir bar, Pd(OCOCF3)2 (4.2 mg, 0.0125 mmol, 5 mol %), (S)-t-BuPyOx (3.1 mg, 0.015 mmol, 6 mol %), and PhB(OH)2 (61 mg, 0.50 mmol, 2.0 equiv). The solids were dissolved in dichloroethane (0.5 mL) and 3-methyl-2-cyclohexenone (29 mL, 0.25 mmol) was added. The walls of the vial were rinsed with an additional portion of dichloroethane (0.5 mL). The vial was capped with a Teflon/silicone septum and stirred at 60 C in an oil bath for 12 h. Upon complete consumption of the starting material (monitored by TLC, 4:1 hexanes/EtOAc, p-anisaldehyde stain) the reaction was purified directly by column chromatography (5:1 hexanes/EtOAc) to afford a clear colorless oil (47 mg, 99% yield).

Reference： [1]Journal of the American Chemical Society,2011,vol. 133,p. 6902 - 6905
[2]Tetrahedron,2015,vol. 71,p. 5781 - 5792
[3]Organic Syntheses,2016,vol. 92,p. 247 - 266

31
[ 129946-88-9 ]
[ 99769-19-4 ]
[ 2557-13-3 ]

Reference： [1]Chemical Communications,2011,vol. 47,p. 4300 - 4302

32
[ 1303588-11-5 ]
[ 99769-19-4 ]
[ 1303588-16-0 ]

Yield	Reaction Conditions	Operation in experiment
92%	With caesium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,2-dimethoxyethane; at 90℃;Inert atmosphere;	Under a nitrogen atmosphere, a mixture of 6-bromo-2,2-dimethyl-3,4-dihydro-2H-pyrido[3,2- b][l,4]oxazine (88; 1.5 g, 6.2 mmol), <strong>[99769-19-4](3-(methoxycarbonyl)phenyl)boronic acid</strong> (1.45 g, 8.0 mmol), Pd(dppf)Cl2 (260 mg, 0.31 mmol,), and cesium carbonate (4.0 g, 12.34 mmol) in dimethoxyethane (50 mL) was stirred at 90 C overnight. The reaction mixture was concentrated and was purified by chromatography, eluting with EtOAc : petroleum ether, to give methyl 3-(2,2-dimethyl-3,4-dihydro-2H-pyrido[3,2-b][l ,4]oxazin-6-yl)benzoate (94; 1.7 g, 92%) as a yellow solid. MS (ESI) calcd for C7H18N2O3: 298.34.

Reference： [1]Patent: WO2011/59839,2011,A1 .Location in patent: Page/Page column 104

33
[ 1248340-80-8 ]
[ 99769-19-4 ]
[ 1335094-21-7 ]

Yield	Reaction Conditions	Operation in experiment
95%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; at 100℃; for 2h;	General procedure: A solution of 2-phenyl-5-methyl-7-chlorobenzo[b]furan 4c (0.100 g, 0.41 mmol), 3-carbomethoxyphenyl boronic acid (0.112 g, 0.62 mmol), Pd2(dba)3 (0.0075 g, 0.0082 mmol), SPhos (0.0067 g, 0.0164 mmol), and K3PO4 (0.261 g, 1.23 mmol) in 1,4-dioxane (2 mL) was stirred at 100 C for 2 h. After cooling, the reaction mixture was dried under reduced pressure and the residue was purified by flash chromatography (SiO2, 50 g; n-hexane/ethyl acetate 90:10 v/v) to give 0.133 g of 5ca 95% yield; mp 130-1 C; IR (KBr) 3100, 1708, 761, 690 cm-1; 1H NMR (CDCl3) delta 8.69 (s, 1H), 8.21 (d, J = 8.0 Hz, 1H), 8.11 (d, J = 7.6 Hz, 1H), 7.89 (d, J = 7.6 Hz, 2H), 6.63 (t, J = 7.6 Hz, 1H), 7.47 (t, J = 7.6 Hz, 2H), 7.40-7.29 (m, 5H), 7.04 (s, 1H), 4.02 (s, 3H), 2.54 (s, 3H); 13CNMR (CDCl3) delta 194.3, 167.1, 156.2, 150.4, 136.9, 133.0, 132.8, 130.6, 130.4, 130.3, 129.6, 128.8, 128.7, 128.61, 128.57, 124.9, 123.5, 120.6, 101.2, 52.2, 21.4; MS m/z (relative intensity) 343 (M+, 100); Anal. Calcd for C23H18O3 C, 80.68; H, 5.30. Found C, 80.59; H, 5.33.
95%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; at 100℃; for 2h;	General procedure: A solution of 2-phenyl-5-methyl-7-chlorobenzo[b]furan 5c (0.100 g, 0.41 mmol), 3-carbomethoxyphenyl boronic acid (0.112 g, 0.62 mmol), Pd2(dba)3 (0.0075 g, 0.0082 mmol), SPhos (0.0067 g, 0.0164 mmol), and K3PO4 (0.261 g,1.23 mmol) in 1,4-dioxane (2 mL) was stirred at 100 C for 2 h. After cooling, the reaction mixture was dried under reduced pressure and the residue was purified by flash chromatography (SiO2, 50 g; n-hexane/ethyl acetate 90:10 v/v) to give 6ca (0.133 g, 95%) as a white solid. Mp: 130-131 C. MS: m/z 365 (MNa+); IR (KBr): 3100,1708, 761, 690 cm-1; 1H NMR(CDCl3): delta 8.69 (s, 1H), 8.21 (d, J¼8.0 Hz, 1H), 8.11 (d, J=7.6 Hz, 1H), 7.89 (d, J=7.6 Hz, 2H), 7.63 (t, J=7.6 Hz,1H), 7.47-7.29 (m, 5H), 7.04 (s,1H), 4.02 (s, 3H), 2.54 (s, 3H); 13C NMR (CDCl3): delta 194.3, 167.1, 156.2, 150.4, 136.9, 133.0, 132.8, 130.6, 130.4, 130.3, 129.6, 128.8, 128.7, 128.61, 128.57, 124.9, 123.5, 120.6, 101.2, 52.2, 21.4. Anal. Calcd for C23H18O3: C, 80.68; H, 5.30. Found: C, 80.60; H, 5.31.

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 5149 - 5152
[2]Tetrahedron,2013,vol. 69,p. 1857 - 1871

34
[ 1335094-11-5 ]
[ 99769-19-4 ]
[ 1335094-16-0 ]

Yield	Reaction Conditions	Operation in experiment
99%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; at 100℃; for 2h;	General procedure: A solution of 2-phenyl-5-methyl-7-chlorobenzo[b]furan 4c (0.100 g, 0.41 mmol), 3-carbomethoxyphenyl boronic acid (0.112 g, 0.62 mmol), Pd2(dba)3 (0.0075 g, 0.0082 mmol), SPhos (0.0067 g, 0.0164 mmol), and K3PO4 (0.261 g, 1.23 mmol) in 1,4-dioxane (2 mL) was stirred at 100 C for 2 h. After cooling, the reaction mixture was dried under reduced pressure and the residue was purified by flash chromatography (SiO2, 50 g; n-hexane/ethyl acetate 90:10 v/v) to give 0.133 g of 5ca 95% yield
99%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; at 100℃; for 2h;	General procedure: A solution of 2-phenyl-5-methyl-7-chlorobenzo[b]furan 5c (0.100 g, 0.41 mmol), 3-carbomethoxyphenyl boronic acid (0.112 g, 0.62 mmol), Pd2(dba)3 (0.0075 g, 0.0082 mmol), SPhos (0.0067 g, 0.0164 mmol), and K3PO4 (0.261 g,1.23 mmol) in 1,4-dioxane (2 mL) was stirred at 100 C for 2 h. After cooling, the reaction mixture was dried under reduced pressure and the residue was purified by flash chromatography (SiO2, 50 g; n-hexane/ethyl acetate 90:10 v/v) to give 6ca (0.133 g, 95%) as a white solid.

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 5149 - 5152
[2]Tetrahedron,2013,vol. 69,p. 1857 - 1871

35
[ 1335094-14-8 ]
[ 99769-19-4 ]
[ 1335094-26-2 ]

Yield	Reaction Conditions	Operation in experiment
99%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; at 100℃; for 2h;	General procedure: A solution of 2-phenyl-5-methyl-7-chlorobenzo[b]furan 4c (0.100 g, 0.41 mmol), 3-carbomethoxyphenyl boronic acid (0.112 g, 0.62 mmol), Pd2(dba)3 (0.0075 g, 0.0082 mmol), SPhos (0.0067 g, 0.0164 mmol), and K3PO4 (0.261 g, 1.23 mmol) in 1,4-dioxane (2 mL) was stirred at 100 C for 2 h. After cooling, the reaction mixture was dried under reduced pressure and the residue was purified by flash chromatography (SiO2, 50 g; n-hexane/ethyl acetate 90:10 v/v) to give 0.133 g of 5ca 95% yield
99%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; at 100℃; for 2h;	General procedure: A solution of 2-phenyl-5-methyl-7-chlorobenzo[b]furan 5c (0.100 g, 0.41 mmol), 3-carbomethoxyphenyl boronic acid (0.112 g, 0.62 mmol), Pd2(dba)3 (0.0075 g, 0.0082 mmol), SPhos (0.0067 g, 0.0164 mmol), and K3PO4 (0.261 g,1.23 mmol) in 1,4-dioxane (2 mL) was stirred at 100 C for 2 h. After cooling, the reaction mixture was dried under reduced pressure and the residue was purified by flash chromatography (SiO2, 50 g; n-hexane/ethyl acetate 90:10 v/v) to give 6ca (0.133 g, 95%) as a white solid.

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 5149 - 5152
[2]Tetrahedron,2013,vol. 69,p. 1857 - 1871

36
[ 1345857-75-1 ]
[ 99769-19-4 ]
[ 1345857-81-9 ]

Yield	Reaction Conditions	Operation in experiment
88%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 105℃; for 21h;Inert atmosphere;	General procedure: K2CO3 (138 mg, 1 mmol) and p-(methoxycarbonyl)phenylboronic acid (135 mg, 0.75 mmol) were dried in vacuo in a Schelenk tube with heating, then bromide 1 (233 mg, 0.5 mmol), and Pd(PPh3)4 (58 mg, 0.05 mmol) were added. The whole system was evacuated and backfilled with argon three times, and 2 mL of DMF was added. The reaction mixture was stirred at room temperature for 1 min, and then conducted at 105 C for 23 h. After the reaction, the mixture was diluted with 15 mL EtOAc, and filtered through a pad of Celite and florisil. Purification by silica gel column chromatography gave 2 (227 mg, 87%) as pale yellow solid materials.

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 6284 - 6287

37
[ 108530-08-1 ]
[ 99769-19-4 ]
[ 177734-95-1 ]

Yield	Reaction Conditions	Operation in experiment
86%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In methanol; water; toluene; for 20h;Reflux;	(i) Methyl 3-(quinolin-8-yl)benzoate 1.04 g (5.77 mmol) of m-(methoxycarbonyl)phenyl boronic acid, 1.00 g (3.67 mmol) of quinolin-8-yl trifluoro-methanesulfonate, 125 mg (0.11 mmol) of tetrakis(triphenylphosphine)palladium(0), and 611 mg (5.77 mmol) of sodium carbonate were heated under reflux in a mixed solvent comprising 4 mL of H2O, 23 mL of toluene, and 6.7 mL of methanol for 20 hours. After the completion of the reaction, the organic solvent was distilled off under reduced pressure, H2O was added to the residue, and ethyl acetate extraction was performed. Subsequently, the organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The obtained crude product was separated and purified by silica gel column chromatography, thereby giving 820 mg of methyl 3-(quinolin-8-yl)benzoate (yield: 86%). 1H-NMR (CDCl3) delta: 3.93 (3H, s), 7.44 (1H, dd, J=8.3, 4.2 Hz), 7.58 (1H, td, J=7.7, 0.3 Hz), 7.62 (1H, dd, J=8.0, 7.2 Hz), 7.76 (1H, dd, J=7.2, 1.6 Hz), 7.87 (1H, dd, J=8.0, 1.6 Hz), 7.94 (1H, ddd, J=7.7, 1.7, 1.3 Hz), 8.10 (1H, ddd, J=7.7, 1.7, 1.3 Hz), 8.23 (1H, dd, J=8.3, 1.8 Hz), 8.37 (1H, td, J=1.7, 0.3 Hz), 8.96 (1H, dd, J=4.2, 1.8 Hz).

Reference： [1]Patent: US2012/22080,2012,A1 .Location in patent: Page/Page column 66

38
[ 1354904-82-7 ]
[ 99769-19-4 ]
[ 1354904-83-8 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium phosphate;tetrakis(triphenylphosphine) palladium(0); In 1-methyl-pyrrolidin-2-one; water; at 150℃; for 0.25h;Microwave irradiation;	Methyl 3-{3-[(2-methyl-4-oxo-3-propyl-3,4-dihydroquinazolin-6- yl)carbonyl]imidazo[1 ,5-a]pyridin-1 -yl}benzoate0.35 g (1 .95 mmol) of 3-methoxycarbonylphenylboronic acid, 0.689 g (3.24 mmol) of potassium phosphate dissolved in 3 ml of water, and 0.037 g (0.032 mmol) of tetrakis(triphenylphosphine)palladium are added to 0.69 g (1 .62 mmol) of 6-[(1 -bromoimidazo[1 ,5-a]pyridin-3-yl)carbonyl]-2-methyl-3- propylquinazolin-4(3/-/)-one in 15 ml of NMP. The reaction medium is microwave- heated for 15 minutes at 150C and then concentrated under reduced pressure. After the addition of 100 ml of water, the precipitate is filtered off and then dried under reduced pressure at 50C overnight. The solid obtained is purified by silica gel column chromatography, elution being carried out with a dichloromethane/methanol (50/1 ) mixture.MH+: 481
	With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In 1-methyl-pyrrolidin-2-one; water; at 150℃; for 0.25h;Microwave irradiation;	Methyl 3-{3-[(2-methyl-4-oxo-3-propyl-3,4-dihydroquinazolin-6- yl)carbonyl]imidazo[1 ,5-a]pyridin-1 -yl}benzoate 0.35 g (1 .95 mmol) of 3-methoxycarbonylphenylboronic acid, 0.689 g (3.24 mmol) of potassium phosphate dissolved in 3 ml of water, and 0.037 g (0.032 mmol) of tetrakis(triphenylphosphine)palladium are added to 0.69 g (1 .62 mmol) of 6-[(1 - bromoimidazo[1 ,5-a]pyridin-3-yl)carbonyl]-2-methyl-3-propylquinazolin-4(3/-/)-one in 15 ml of NMP. The reaction medium is microwave-heated for 15 minutes at 150C and then concentrated under reduced pressure. After the addition of 100 ml of water, the precipitate is filtered off and then dried under reduced pressure at 50C overnight. The solid obtained is purified by silica gel column chromatography, elution being carried out with a dichloromethane/methanol (50/1 ) mixture. MH+: 481

Reference： [1]Patent: WO2012/4732,2012,A1 .Location in patent: Page/Page column 36
[2]Patent: WO2013/102860,2013,A1 .Location in patent: Page/Page column 43; 44
[3]Patent: EP2800566,2015,B1 .Location in patent: Paragraph 0091

39
[ 99769-19-4 ]
[ 154607-00-8 ]
[ 1393439-87-6 ]

Yield	Reaction Conditions	Operation in experiment
84%	With tetrabutylammomium bromide; potassium carbonate;palladium diacetate; In water; at 70℃; for 1.33333h;Microwave irradiation; Sealed tube;	Methyl 2-(3-methoxycarbonylphenyl)-5-[(2/?,3S,4S,5S,6 ?)-3,4,5- trihydroxy-6-(hydroxymethyl)tetrahydropyran-2-yl]oxy-benzoate (6). Methyl 5- hydroxy-2-(3-methoxycarbonylphenyl)benzoate: The reactants of methyl 2-bromo-5- hydroxybenzoate (0.231 g, 1 mmol), 3-methoxycarbonylphenyl boronic acid (0.214 g,1.2 mmol), palladium acetate (0.022g, 0.1 mmol), potassium carbonate (0.346 g, 2.5 mmol) and tetrabutylammonium bromide (0.322 g, 1 mmol) in 1.2 ml of water was heated with stirring at 70 C for 1 h and 20 mins in a sealed vial by microwave. Then the mixture was partitioned between AcOEt and 1 N HCI aqueous solution. The organic layer was collected, dried with Na2S04, then concentrated. The resulting residue was purified by silica gel chromatography with AcOEt/Hex combinations as eluent, giving the title compound (0.240 g) in 84% yield. 1H NMR (300 MHz, DMSO-d6) delta ppm 10.02 (s,1 H), 7.90 (td, J = 2.03, 6.66 Hz, 1 H), 7.72 - 7.81 (m, 1 H), 7.45 - 7.60 (m, 2H), 7.28 (d, J = 8.52 Hz, 1 H), 7.16 (d, J = 2.47 Hz, 1 H), 7.03 (dd, J = 2.61 , 8.38 Hz, 1 H), 3.86 (s, 3H), 3.56 (s, 3H). MS (ESI): found [M + Na]+, 309.2.

Reference： [1]Journal of Medicinal Chemistry,2012,vol. 55,p. 3945 - 3959
[2]Patent: WO2012/109263,2012,A1 .Location in patent: Page/Page column 96-97

40
[ 99769-19-4 ]
[ 90971-88-3 ]
[ 378242-15-0 ]

Reference： [1]Journal of Medicinal Chemistry,2012,vol. 55,p. 5922 - 5932

41
[ 99769-19-4 ]
potassium hexacyanoferrate(III) [ No CAS ]
[ 13531-48-1 ]

Reference： [1]Chemistry Letters,2012,vol. 41,p. 719 - 721

42
[ 1278250-11-5 ]
[ 99769-19-4 ]
[ 1278652-51-9 ]

Yield	Reaction Conditions	Operation in experiment
90%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate; In tetrahydrofuran; water;	9.1 methyl 3-[2-(4-chlorophenyl)pyrazolo[1,5-a]pyridin-5-yl]benzoate[0141]The procedure described in Example 3 is followed. Starting from 1.5 g (4.88 mmol) of 5-bromo-2-(4-chlorophenyl)pyrazolo[1,5-a]pyridine, obtained according to the protocol described in Examples 1.3 or 2.3, 1.05 mg (5.83 mmol) of 3-methoxycarbonylphenylboronic acid, 4.6 g (14.61 mmol) of caesium carbonate, 0.400 g (0.49 mmol) of [1,1?-bis(diphenyl-phosphino)ferrocene]dichloropalladium(II) and 20 ml of a THF/water (9/1) mixture and after chromatographing on silica gel, elution being carried out with a mixture of cyclohexane and ethyl acetate (9/1), 1.6 g (90%) of the expected product are obtained in the form of a yellow-white powder.[0142]Melting point ( C.): 180-182[0143]LC-MS: M+H=363[0144]1H NMR (d6-DMSO) delta (ppm): 3.95 (s, 3H); 7.20 (s, 1H); 7.35 (d, 1H); 7.60 (d, 2H); 7.70 (t, 1H); from 8.00 to 8.20 (m, 5H); 8.35 (s, 1H); 8.85 (d, 1H).
72%	With caesium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In tetrahydrofuran; water; at 70℃; for 1.5h;	1.4 Methyl 3-[2-(4-chlororophenyl)pyrazolo[1,5-a]pyridin-5-yl]benzoate 0.235 g (0.76 mmol) of 5-bromo-2-(4-chlorophenyl)pyrazolo[1,5-a]pyridine obtained in step 1.3, 0.165 g (0.92 mmol) of 3-methoxycarbonylphenylboronic acid, 0.750 g (2.30 mmol) of caesium carbonate and 0.065 g (0.08 mmol) of [1,1'-bis(diphenylphosphino)-ferrocene]dichloropalladium (II) are placed in a round-bottomed flask in the presence of 5 mL of a THF-water mixture (9/1). The medium is then maintained at 70 C. for 1 hour 30 minutes, and is then cooled to room temperature and diluted with 30 mL of dichloromethane and 30 mL of water. The two-phase medium is filtered on a hydrophobic cartridge (Radleys 70 mL liquid/liquid extraction column) and the filtrate is then concentrated under reduced pressure: the residue obtained is chromatographed on silica gel, eluting with a mixture of cyclohexane and ethyl acetate (8/2). 0.200 g (72%) of expected compound is obtained in the fottu of a beige powder. Melting point ( C.): 180-182 LC-MS: M+H=363 1H NMR (DMSO) delta (ppm): 3.95 (s, 3H); 7.20 (s, 1H); 7.35 (d, 1H); 7.60 (d, 2H); 7.70 (t, 1H); from 8.00 to 8.20 (m, 5H); 8.35 (s, 1H); 8.85 (d, 1H).

Reference： [1]Patent: US2013/23554,2013,A1 .Location in patent: Paragraph 0141
[2]Patent: US2012/245164,2012,A1 .Location in patent: Page/Page column 6

43
[ 1278250-15-9 ]
[ 99769-19-4 ]
[ 1278652-52-0 ]

Yield	Reaction Conditions	Operation in experiment
71%	With caesium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In tetrahydrofuran; water; at 70℃; for 4h;Inert atmosphere;	5.4 methyl 3-[2-(4-fluorophenyl)pyrazolo[1,5-a]pyridin-5-yl]benzoate Under a stream of nitrogen, 0.400 g (1.37 mmol) of 5-bromo-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridine obtained in step 5.3, 0.300 g (1.67 mmol) of 3-methoxycarbonylphenylboronic acid and 1.330 g (4.08 mmol) of caesium carbonate are placed in 5 mL of a 9/1 mixture of tetrahydrofuran and water. 0.11 g (0.13 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (II) is added and the medium is heated at 70 C. for 4 hours. The medium is then cooled to room temperature and diluted with 40 mL of dichloromethane and 40 mL of water. The medium is then filtered on a hydrophobic cartridge (Radleys 70 mL liquid/liquid extraction column) and the organic phase is recovered and concentrated under reduced pressure after addition of 2 g of silica. The residue is purified by chromatography on silica gel, eluting with a mixture of cyclohexane and ethyl acetate (9/1). 0.340 g (71%) of expected product is obtained in the form of a white powder. Melting point ( C.): 162-164 LC-MS: M+H=347 1H NMR (DMSO) delta (ppm): 3.95 (s, 3H); 7.15 (s, 1H); from 7.30 to 7.38 (m, 3H); 7.70 (t, 1H); from 8.00 to 8.15 (m, 5H); 8.35 (m, 1H); 8.80 (d, 1H).
71%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate; In tetrahydrofuran; water; at 70℃; for 4h;Inert atmosphere;	EXAMPLE 10 2-{3-[2-(4-fluorophenyl)pyrazolo[1,5-a]pyridin-5-yl]phenyl}propan-2-ol (Compound 7 of the Table) 10.1 methyl 3-[2-(4-fluorophenyl)pyrazolo[1,5-a]pyridin-5-yl]benzoate 0.400 g (1.37 mmol) of 5-bromo-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridine, obtained in stage 5.3, 0.300 g (1.67 mmol) of 3-methoxycarbonylphenylboronic acid and 1.330 g (4.08 mmol) of caesium carbonate are introduced under a stream of nitrogen into 5 ml of a 9/1 mixture of tetrahydrofuran and water. 0.11 g (0.13 mmol) of [1,1'-bis(diphenyl-phosphino)ferrocene]dichloropalladium(II) is added and the medium is heated at 70 C. for 4 hours. The medium is subsequently brought back to ambient temperature and then diluted with 40 ml of dichloromethane and 40 ml of water. The medium is subsequently filtered through a hydrophobic cartridge (70 ml liquid/liquid extraction column, Radleys) and the organic phase is recovered and concentrated under reduced pressure after having added 2 g of silica. The residue is purified by chromatography on silica gel, elution being carried out with a mixture of cyclohexane and ethyl acetate (9/1). 0.340 g (71%) of the expected product is obtained in the form of a white powder. LC-MS: M+H=347 1H NMR (d6-DMSO) delta (ppm): 3.95 (s, 3H); 7.15 (s, 1H); from 7.30 to 7.40 (m, 3H); 7.70 (t, 1H); from 8.00 to 8.15 (m, 5H); 8.35 (s, 1H); 8.80 (d, 1H).

Reference： [1]Patent: US2012/245164,2012,A1 .Location in patent: Page/Page column 8
[2]Patent: US2013/23554,2013,A1 .Location in patent: Paragraph 0149; 0150

44
[ 585-70-6 ]
[ 99769-19-4 ]
[ 874999-81-2 ]

Yield	Reaction Conditions	Operation in experiment
91%	With sodium hydrogencarbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; toluene; at 90℃; for 2h;	To 5-bromofuran-2-carboxylic acid (0.50 g, 2.6 mmol), 3-methoxycarbonylphenylboronic acid (0.52 g, 2.9 mmol), tetrakis(triphenylphosphine)palladium (45 mg, 0.039 mmol) and sodium hydrogen carbonate (0.49 g, 5.9 mmol) were added toluene (3.5 mL), tetrahydrofuran (3.0 mL) and water (3.5 mL), and the mixture was stirred at 90C for 2 hr. Water was added to the reaction mixture, and the mixture was washed with ethyl acetate. The aqueous layer was acidified with 1N hydrochloric acid, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure to give the title compound as a pale-yellow powder (0.58 g, 2.3 mmol, 91%). 1H-NMR(400MHz, CDCl3) delta 8.44(1H, d, J=1.6Hz), 8.06-8.01(2H, m), 7.54(1H, dd, J=8.0, 7.6Hz), 7.42(1H, d, J=3.6Hz), 6.89(1H, d, J=3.6Hz), 3.97(3H, s). MS(ESI) m/z 247(M+H)+

Reference： [1]Patent: EP2511271,2012,A1 .Location in patent: Page/Page column 45

45
[ 53595-65-6 ]
[ 99769-19-4 ]
[ 1176724-02-9 ]

Yield	Reaction Conditions	Operation in experiment
53%	With potassium phosphate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; N,N-dimethyl-formamide; at 85℃;Inert atmosphere;	(1) 1,1'-Bis(diphenylphosphino)ferrocene-palladium(II) dichloride-dichloromethane complex (272 mg, 0.33 mmol), 3-methoxycarbonylphenylboronic acid (898 mg, 4.99 mmol), and tripotassium phosphate (1.41 g, 6.64 mmol) were added to a solution of commercially available 5-bromothiophene-2-sulfonamide (805 mg, 3.33 mmol) in mixture of 1,4-dioxane (10 mL) and DMF (1 mL), followed by stirring at 85C overnight in an argon atmosphere. The reaction solution was concentrated. A saturated aqueous solution of sodium chloride was added to the residue, followed by extraction with methylene chloride and drying over anhydrous sodium sulfate. The solvent was distilled off, and methanol was added to the residue. The precipitated solid was filtered off. The residue obtained by distilling the solvent off was subjected to purification by silica gel column chromatography to obtain 3-(5-sulfamoyl-2-thienyl)benzoic acid methyl ester (529 mg, 1.78 mmol) (yield: 53%). ES-MS (m/z): 296 (M-H)-.

Reference： [1]Patent: EP2520575,2012,A1 .Location in patent: Page/Page column 68

46
[ 491-38-3 ]
[ 99769-19-4 ]
[ 1438762-93-6 ]

Yield	Reaction Conditions	Operation in experiment
34.1%		Example 8A ( ?)-methyl 3 -(4-oxochroman-2-yl)benzoate A 20 mL vial was charged with bis(2,2,2-trifluoroacetoxy)palladium (56.9 mg, 0.171 mmol), (S)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole (41.9 mg, 0.205 mmol), ammonium hexafluorophosphate(V) (167 mg, 1.026 mmol), and 3- methoxycarbonylphenylboronic acid (1231 mg, 6.84 mmol). The reaction was stirred in dichloroethane (5 mL) for 5 minutes, and a pale yellow color was observed. To this suspension was added 4H-chromen-4-one (CAS 11013-97-1) (500 mg, 3.42 mmol) and water (0.308 mL, 17.11 mmol) and the sides of the vial washed with more dichloroethane (5 mL). The vial was capped and the mixture stirred at 60 C for 16 hours. The mixture was filtered through a plug of silica gel and celite and eluted with ethyl acetate to give a red solution. The solvent was removed and the crude material was chromatographed using a 40g silica gel cartridge with a gradient of 5-50 % ethyl acetate/heptanes over 40 minutes to give the title compound (329 mg, 1.165 mmol, 34.1 % yield) as a white solid. 1H NMR (400 MHz, DMSO-d6) delta 8.16 (t, J = 1.8 Hz, 1H), 7.98 (dt, J = 7.7, 1.5 Hz, 1H), 7.84 (dt, J = 7.9, 1.4 Hz, 1H), 7.81 (dd, J = 7.8, 1.8 Hz, 1H), 7.65 - 7.58 (m, 2H), 7.17 - 7.10 (m, 2H), 5.80 (dd, J = 13.1, 2.8 Hz, 1H), 3.88 (s, 3H), 3.28 (dd, J = 16.8, 13.1 Hz, 1H), 2.88 (dd, J = 16.8, 3.0 Hz, 1H); MS (ESI+) m/z 300 (M+NH4)+.
34.1%		Example 21A methyl 3-[(2R)-4-oxo-3,4-dihydro-2H-1-benzopyran-2-yl]benzoate A 20 mL vial was charged with bis(2,2,2-trifluoroacetoxy)palladium (56.9 mg, 0.171 mmol), (S)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole (41.9 mg, 0.205 mmol), ammonium hexafluorophosphate(V) (167 mg, 1.026 mmol), and 3-methoxycarbonylphenylboronic acid (1231 mg, 6.84 mmol). The mixture was stirred in dichloroethane (5 mL) for 5 minutes. To this suspension was added 4H-chromen-4-one (CAS 11013-97-1) (500 mg, 3.42 mmol) and water (0.308 mL, 17.11 mmol), and the sides of the vial were washed with more dichloroethane (5 mL). The vial was capped, and the mixture stirred at 60 C. for 16 hours. The mixture was filtered through a plug of silica gel and diatomaceous earth eluted with ethyl acetate. The filtrate was concentrated, and the crude material was chromatographed using a 40 g silica gel cartridge with a gradient of 5-50% ethyl acetate/heptanes over 40 minutes to give the title compound (329 mg, 1.165 mmol, 34.1% yield). 1H NMR (400 MHz, DMSO-d6) delta ppm 8.16 (t, J=1.8 Hz, 1H), 7.98 (dt, J=7.7, 1.5 Hz, 1H), 7.84 (dt, J=7.9, 1.4 Hz, 1H), 7.81 (dd, J=7.8, 1.8 Hz, 1H), 7.65-7.58 (m, 2H), 7.17-7.10 (m, 2H), 5.80 (dd, J=13.1, 2.8 Hz, 1H), 3.88 (s, 3H), 3.28 (dd, J=16.8, 13.1 Hz, 1H), 2.88 (dd, J=16.8, 3.0 Hz, 1H); MS (ESI+) m/z 300 (M+NH4)+.

Reference： [1]Chemistry - A European Journal,2013,vol. 19,p. 74 - 77
[2]Patent: WO2016/69757,2016,A1 .Location in patent: Page/Page column 131
[3]Patent: US2017/15675,2017,A1 .Location in patent: Paragraph 0989
[4]Journal of Medicinal Chemistry,2018,vol. 61,p. 1436 - 1449

47
[ 5751-52-0 ]
[ 99769-19-4 ]
methyl 3-(7-methoxy-4-oxochroman-2-yl)benzoate [ No CAS ]

Reference： [1]Chemistry - A European Journal,2013,vol. 19,p. 74 - 77

48
[ 5751-52-0 ]
[ 99769-19-4 ]
[ 1438761-56-8 ]

Yield	Reaction Conditions	Operation in experiment
75%		Example 5B (i?)-methyl 3 -(7-methoxy-4-oxochroman-2-yl)benzoate A 4 mL vial was charged with bis(2,2,2-trifluoroacetoxy)palladium (9.44 mg, 0.028 mmol), (5)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole (6.96 mg, 0.034 mmol), ammonium hexafluorophosphate(V) (27.8 mg, 0.170 mmol), and 3- methoxycarbonylphenylboronic acid (204 mg, 1.135 mmol) were stirred in dichloroethane (1.0 mL) for 5 minutes, and a pale yellow color was observed. To this suspension was added Example 5A (100 mg, 0.568 mmol) and water (0.051 mL, 2.84 mmol) and the sides of the vial washed with more dichloroethane (1.0 mL). The vial was capped and the mixture stirred at 60 C overnight. The mixture was filtered through a plug of silica gel and eluted with dichloromethane and then ethyl acetate. The solvent was removed and the crude material was chromatographed using a 12g silica gel cartridge with a gradient of 5-50 % ethyl acetate/heptanes over 20 minutes to give the title compound (133 mg, 0.426 mmol, 75 % yield) as a white solid. 1H NMR (400 MHz, DMSO-d6) delta 8.15 (t, J = 1.8 Hz, 1H), 7.98 (dt, J = 7.8, 1.4 Hz, 1H), 7.84 (dt, J = 7.9, 1.5 Hz, 1H), 7.74 (d, J = 8.5 Hz, 1H), 7.61 (t, J = 7.8 Hz, 1H), 6.69 (d, J = 8.6 Hz, 2H), 5.77 (dd, J = 12.9, 2.9 Hz, 1H), 3.88 (s, 3H), 3.83 (s, 3H), 3.17 (dd, J = 16.8, 13.0 Hz, 1H), 2.80 (dd, J = 16.8, 3.0 Hz, 1H); MS (ESI+) m/z 313 (M+H)+.
75%		Example 10B methyl 3-[(2R)-7-methoxy-4-oxo-3,4-dihydro-2H-1-benzopyran-2-yl]benzoate A 4 mL vial was charged with bis(2,2,2-trifluoroacetoxy)palladium (9.44 mg, 0.028 mmol), (S)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole (6.96 mg, 0.034 mmol), ammonium hexafluorophosphate(V) (27.8 mg, 0.170 mmol), and 3-methoxycarbonylphenylboronic acid (204 mg, 1.135 mmol), and the mixture was stirred in dichloroethane (1.0 mL) for 5 minutes. To this suspension was added Example 10A (100 mg, 0.568 mmol) and water (0.051 mL, 2.84 mmol), and the sides of the vial were washed with more dichloroethane (1.0 mL). The vial was capped and the mixture stirred at 60 C. overnight. The mixture was filtered through a plug of silica gel eluted with dichloromethane and then ethyl acetate. The filtrate was concentrated, and the crude material was chromatographed using a 12 g silica gel cartridge with a gradient of 5-50% ethyl acetate/heptanes over 20 minutes to give the title compound (133 mg, 0.426 mmol, 75% yield). 1H NMR (400 MHz, DMSO-d6) delta ppm 8.15 (t, J=1.8 Hz, 1H), 7.98 (dt, J=7.8, 1.4 Hz, 1H), 7.84 (dt, J=7.9, 1.5 Hz, 1H), 7.74 (d, J=8.5 Hz, 1H), 7.61 (t, J=7.8 Hz, 1H), 6.69 (d, J=8.6 Hz, 2H), 5.77 (dd, J=12.9, 2.9 Hz, 1H), 3.88 (s, 3H), 3.83 (s, 3H), 3.17 (dd, J=16.8, 13.0 Hz, 1H), 2.80 (dd, J=16.8, 3.0 Hz, 1H); MS (ESI+) m/z 313 (M+H)+.
75%	With ammonium hexafluorophosphate; palladium(II) trifluoroacetate; 2-[(S)-4,5-dihydro-4-tert-butyl-1,3-oxazol-2-yl]pyridine; In water; 1,2-dichloro-ethane; at 60℃;	A 4 mL vial was charged with bis(2,2,2-trifluoroacetoxy)palladium (9.44 mg, 0.028 mmol), (S)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole (6.96 mg, 0.034 mmol), ammonium hexafluorophosphate(V) (27.8 mg, 0.170 mmol), and 3-methoxycarbonylphenylboronic acid (204 mg, 1.135 mmol), and the mixture was stirred in dichloroethane (1.0 mL) for 5 minutes. To the mixture was added Example 7D (100 mg, 0.568 mmol) and water (0.051 mL, 2.84 mmol), and the sides of the vial were washed with more dichloroethane (1.0 mL). The vial was capped and the mixture stirred at 60 C. overnight. The mixture was filtered through a plug of silica gel, and eluted with dichloromethane and ethyl acetate. The filtrate was concentrated, and the crude material was chromatographed using a 12 g silica gel cartridge with a gradient of 5-50% ethyl acetate/heptanes over 20 minutes to provide the title compound (133 mg, 0.426 mmol, 75% yield). 1H NMR (400 MHz, dimethyl sulfoxide-d6) delta ppm 8.15 (t, J=1.8 Hz, 1H), 7.98 (dt, J=7.8, 1.4 Hz, 1H), 7.84 (dt, J=7.9, 1.5 Hz, 1H), 7.74 (d, J=8.5 Hz, 1H), 7.61 (t, J=7.8 Hz, 1H), 6.69 (d, J=8.6 Hz, 2H), 5.77 (dd, J=12.9, 2.9 Hz, 1H), 3.88 (s, 3H), 3.83 (s, 3H), 3.17 (dd, J=16.8, 13.0 Hz, 1H), 2.80 (dd, J=16.8, 3.0 Hz, 1H); MS (ESI+) m/z 313 (M+H)+.

Reference： [1]Chemistry - A European Journal,2013,vol. 19,p. 74 - 77
[2]Patent: WO2016/69757,2016,A1 .Location in patent: Page/Page column 128
[3]Patent: US2017/15675,2017,A1 .Location in patent: Paragraph 0971
[4]Patent: US2017/305891,2017,A1 .Location in patent: Paragraph 0741
[5]Journal of Medicinal Chemistry,2018,vol. 61,p. 1436 - 1449

49
[ 1314263-85-8 ]
[ 99769-19-4 ]
[ 1314258-15-5 ]

Yield	Reaction Conditions	Operation in experiment
53%		Synthetic method A [00211] Example 1 : 3-(2-phenyl-4-(pyridin-4-yl)-lH-imidazol-5-yl)benzoic acid[00212] A microwave vessel was charged with 5-bromo-2-phenyl-4-(pyridin-4-yl)- lH-imidazole (100 mg, 0.333 mmol), 3-methoxycarbonylphenylboronic acid (90 mg, 0.5 mmol), PdCl2(PPh3)2 (12 mg, 0.017 mmol), and potassium carbonate (276 mg, 2 mmol) under nitrogen atmosphere. Degassed DME (3.2 mL) and water (0.8 mL) were added. The vessel was capped and micro waved at 150C for 30 min. in a Biotage Initiator microwave instrument. A IN aqueous solution of KOH (3 mL) was added and the mixture was further stirred overnight. The reaction mixture was filtered through celite and the filtrate was extracted with EtOAc (3x). The aqueous layer was isolated and acidified to pH 4.5 with concentrated HCl. The resulting precipitate was filtered, washed with water, and dried in vacuo to give 60 mg of the title compound as a yellow solid (53% yield).

Reference： [1]Patent: WO2011/85269,2011,A1 .Location in patent: Page/Page column 76

50
[ 1283092-22-7 ]
[ 99769-19-4 ]
[ 1314258-26-8 ]

Yield	Reaction Conditions	Operation in experiment
69%		Synthetic method C[00216] Example 3 : 3-(l-phenyl-3-(pyridin-4-yl)-lH-pyrazol-4-yl)benzoic acid [00217] A microwave vessel was charged with 4-bromo-l-phenyl-3-(pyridin-4-yl)- lH-pyrazole (50 mg, 0.167 mmol), 3-methoxycarbonylphenylboronic acid (33 mg, 0.183 mmol), PdCl2(PPh3)2 (6 mg, 0.008 mmol) under nitrogen atmosphere. 1 ,4-Dioxane (0.5 mL) and saturated aqueous sodium carbonate (0.5 mL) were added. The vessel was capped and micro waved at 150C for 30 min. in a Biotage Initiator microwave instrument. The reaction mixture was diluted with IN aqueous KOH (3 mL), filtered through celite, and the filtrate was extracted with EtOAc (3x). The aqueous layer was isolated and acidified to pH 4.5 with concentrated HC1. The resulting precipitate was filtered, washed with water, and dried in vacuo to give 39 mg of the title compound as a light beige solid (69% yield).

Reference： [1]Patent: WO2011/85269,2011,A1 .Location in patent: Page/Page column 77-78

51
[ 99769-19-4 ]
[ 455-68-5 ]

Reference： [1]Journal of the American Chemical Society,2013,vol. 135,p. 2552 - 2559

52
[ 76-09-5 ]
[ 99769-19-4 ]
[ 480425-35-2 ]

Reference： [1]Journal of the American Chemical Society,2013,vol. 135,p. 2552 - 2559
[2]Organic Letters,2015,vol. 17,p. 3086 - 3089
[3]Angewandte Chemie - International Edition,2019,vol. 58,p. 6554 - 6558
Angew. Chem.,2019,vol. 131,p. 6626 - 6630,5

53
[ 1422250-63-2 ]
[ 99769-19-4 ]
[ 1422250-76-7 ]

Yield	Reaction Conditions	Operation in experiment
99%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; at 100℃; for 3h;	General procedure: A solution of 2-phenyl-5-methyl-7-chlorobenzo[b]furan 5c (0.100 g, 0.41 mmol), 3-carbomethoxyphenyl boronic acid (0.112 g, 0.62 mmol), Pd2(dba)3 (0.0075 g, 0.0082 mmol), SPhos (0.0067 g, 0.0164 mmol), and K3PO4 (0.261 g,1.23 mmol) in 1,4-dioxane (2 mL) was stirred at 100 C for 2 h. After cooling, the reaction mixture was dried under reduced pressure and the residue was purified by flash chromatography (SiO2, 50 g; n-hexane/ethyl acetate 90:10 v/v) to give 6ca (0.133 g, 95%) as a white solid.

Reference： [1]Tetrahedron,2013,vol. 69,p. 1857 - 1871

54
[ 58556-75-5 ]
[ 99769-19-4 ]
[ 1426343-41-0 ]

Reference： [1]Patent: WO2013/29830,2013,A1

55
[ 58556-75-5 ]
[ 99769-19-4 ]
[ 1426343-42-1 ]

Yield	Reaction Conditions	Operation in experiment
72%	With tetrakis(triphenylphosphine) palladium(0); cesium fluoride; In 1,2-dimethoxyethane; for 48h;Inert atmosphere; Reflux; Schlenk technique;	(a) Dimethyl 3,3'-(naphthalene-2,7-diyl)dibenzoateTo a 250 mL Schlenk flask, <strong>[58556-75-5]2,7-dibromonaphthalene</strong> (2.00 g, 6.99 mmol), 3- (methoxycarbonyl)phenylboronic acid (3.15 g, 17.48 mmol), CsF (4.00 g) and Pd(PPh3)4 (200 mg) were added. The flask was connected to a Schlenk line and evacuated of air then refilled with nitrogen. 150 mL of 1,2-dimethoxyethane (DME) was degassed (two hours) and added to the flask through a canula. The flask was equipped with a water condenser and refluxed under nitrogen for 2 days. The solvent was removed on a rotary evaporator. 100 mL of H20 was added and then extracted with CHC13. The organic phase was dried with MgS04. After removal of the CHC13 solvent, the crude product was re- crystallized from the mixture solvent of ethyl acetate and hexane (v/v = 1:9) to give a pure product with a yield of 72% (2.0 g) based on <strong>[58556-75-5]2,7-dibromonaphthalene</strong>. ? NMR (300 MHz, DMSO-d6): delta 3.92 (s, 6H), 7.70 (t, 2H), 7·93 (d, 2H), 8.01 (d, 2H), 8.13 (m, 4H), 8.39 (m, 2H), 8.45 (d, 2H).

Reference： [1]Patent: WO2013/29830,2013,A1 .Location in patent: Page/Page column 21
[2]Chemistry - A European Journal,2019,vol. 25,p. 5186 - 5201

56
[ 99769-19-4 ]
[ 63555-50-0 ]

Reference： [1]Journal of the American Chemical Society,2013,vol. 135,p. 10638 - 10641

57
[ 99769-19-4 ]
[ 455-68-5 ]
[ 618-91-7 ]

Reference： [1]Organic Letters,2013,vol. 15,p. 5134 - 5137

58
[ 16494-36-3 ]
[ 99769-19-4 ]
[ 177735-17-0 ]

Reference： [1]ChemMedChem,2014,vol. 9,p. 657 - 664

59
[ 57455-06-8 ]
[ 99769-19-4 ]
[ 889955-78-6 ]

Yield	Reaction Conditions	Operation in experiment
100%	With palladium diacetate; sodium carbonate; In water; N,N-dimethyl-formamide; at 55℃; for 1.5h;	1M ofaqueous Na2CO3 (34 mL) solution was added to3-iodo-benzyl alcohol 13 (2.72g, 11.6mmol) and 3- (methoxycarbonyl) phenylboronic acid (14) (2.009, 11.1 mmol) and DMF (7 mL ) solution of Pd (OAc)2 (56.2ng, 0.250 mmol) and was heated at 55 C for 1.5 hours. Thereaction solution was diluted with chloroform and filtered. Then the chloroformlayer was separated, and after washed with water and brine, it was dried overanhydrous sodium sulfate. Furthermore, it was vacuum concentrated, and purifiedby silica gel flash column (eluent 0-80% ethyl acetate / n-hexane) to obtain 3.85g of compound 15 as a pale brown oil.

Reference： [1]ChemMedChem,2014,vol. 9,p. 657 - 664
[2]Patent: JP2016/17040,2016,A .Location in patent: Paragraph 0018; 0019

60
[ 52605-98-8 ]
[ 99769-19-4 ]
C₁₅H₁₅NO₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 100℃; for 16h;	c. Preparation of Compound A mixture of <strong>[52605-98-8]5-bromo-2,3-dimethoxypyridine</strong> (520 mg, 2.39 mmol) ,3- carbomethoxyphenylboronic acid (560 mg, 3.12 mmol), Pd(PPh3)4 (346 mg, 0.3 mmol) and K2CO3 (657 mg, 4.76 mmol) in 1,4- dioxane (5.0 ml) and H20 (1.5 ml) was degassed for 30 min. This mixture was heated to 100 C and stirred for 16 h. The reaction mixture was cooled to room temperature and partitioned between NaHC03 and EtOAc (3x), and washed with NaCl (lx). The organic phase was dried over Na2S04 and was concentrated. The resulting residue was purified by ISCO flash chromatography using DCM to give 540 mg (83% yield) desired product. 1H NMR (300 MHz, CDC13) delta: 8.21 (s, 1H), 8.02 ( d, J = 7.8 Hz, 1H), 7.97 (d, J = 1.8 Hz, 1H), 7.73 (d, J = 6.6 Hz, 1H), 7.52 (t, 1H), 7.27 (d, J = 1,2 Hz, 1H), 4.07 (s, 3H), 3.96 (s, 3H), 3.95 (s, 3H).

Reference： [1]Patent: WO2014/43252,2014,A2 .Location in patent: Page/Page column 101

61
[ 99769-19-4 ]
[ 4467-07-6 ]

Reference： [1]Patent: WO2014/100734,2014,A1
[2]ACS Medicinal Chemistry Letters,2016,vol. 7,p. 162 - 166

62
[ 59557-90-3 ]
[ 99769-19-4 ]
4'-amino-2',6'-dimethyl-[1,1'-biphenyl]-3-carboxylic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate; In water; N,N-dimethyl-formamide; at 90℃; for 1h;	Step) 4'-amino-2',6'-dimethyl-[1,1'-biphenyl] -3-carboxylate<strong>[59557-90-3]4-bromo-3,5-dimethylaniline</strong> (lg, lOmmol), (3- (methoxycarbonyl) phenyl) borate (2 · 7g, 15mmol), potassium carbonate (4 · 14g, 30mmol), [ 1,1 '- bis (diphenylphosphino) ferrocene] dichloropalladium dichloromethane complex (. 0. 37g, 0 5mmol) was dissolved in N, N-dimethylformamide (30mL) and water (10mL), and stirred at 90 C for 1 hour. The reaction was cooled to room temperature and added water (30 mL) was diluted with ethyl acetate (200mL X 2), the combined organic phase was washed with saturated sodium chloride solution (50 mL), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (petroleum ether: ethyl acetate = 4: 1) to give the title compound as a pale yellow solid (2. 1g, 82% yield).
82%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate; In N,N-dimethyl-formamide; at 90℃; for 1h;	A mixture of <strong>[59557-90-3]4-bromo-3,5-dimethylaniline</strong> (1 g, 10 mmol), (3- (methoxycarbonyl) phenyl) boronic acid (2.7 g, 15 mmol), potassium carbonate (4.14 g, 30 mmol) , Bis (diphenylphosphino) ferrocene] dichloropalladium dichloromethane complex (0.37 g, 0.5 mmol) was dissolved in N, N-dimethylformamide (30 mL) and water 10 mL), and the reaction was stirred at 90 C for 1 hour.The reaction mixture was cooled to room temperature, diluted with water (30 mL) and extracted with ethyl acetate (200 mL × 2). The combined organic layers were washed with saturated sodium chloride solution (50 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure filtrate.The residue was purified by silica gel column chromatography (petroleum ether: ethyl acetate = 4: 1) to give the title compound (2.1 g, yield 82%) as a pale yellow solid.
82%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate; In water; N,N-dimethyl-formamide; at 90℃; for 1h;	<strong>[59557-90-3]4-bromo-3,5-dimethylaniline</strong> (1g, 10mmol), (3-(methoxycarbonyl)phenyl)boronic acid (2.7g, 15mmol), potassium carbonate (4.14g, 30mmol), 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium(II) dichloromethane (0.37g, 0.5mmol) dissolved in N,N-dimethylformamide (30 ml) and water (10 ml). At 90 C, stirring for 1 hour. The reaction is cooled down to the room temperature after the addition of water (30 ml) after diluting the extraction of ethyl acetate (200 ml × 2), combined with the organic phase, saturated sodium chloride solution (50 ml), anhydrous sodium sulfate drying, filtering, the filtrate is concentrated under reduced pressure. The residue is purified silica gel column chromatography (petroleum ether: ethyl acetate=4:1), to obtain light yellow solid title compound (2.1g, yield 82%).

Reference： [1]Patent: WO2015/62486,2015,A1 .Location in patent: Paragraph 00318
[2]Patent: CN104177320,2016,B .Location in patent: Paragraph 0150; 0152; 0153
[3]Patent: CN104262330,2016,B .Location in patent: Paragraph 0152-0155
[4]Patent: CN104193731,2017,B .Location in patent: Paragraph 0146; 0147

63
2-chloro-5-(3,5-dimethylisoxazol-4-yl)pyridin-3-amine [ No CAS ]
[ 99769-19-4 ]
methyl 3-((2-chloro-5-(3,5-dimethylisoxazol-4-yl)pyridin-3-yl)amino)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
57%	With pyridine; oxygen; copper diacetate; In chloroform; at 20℃;Molecular sieve;	Step 2: Methyl 3-((2-chloro-5-(3,5-dimethylisoxazol-4-yl)pyridin-3- yl)amino)benzoateTo a 250 mL round bottom flask containing 2-chloro-5-(3,5-dimethylisoxazol-4- yl)pyridin-3 -amine (2.0 g, 8.9 mmol), (3 -(methoxycarbonyl)phenyl)boronic acid (Aldrich,3.22 g, 17.9 mmol), Cu(OAc)2 (2.43 g, 13.4 mmol) and powdered 4A molecular sieves (7.0 g) was added CHC13 (50 mL) and pyridine (1.45 mL, 17.9 mL). The atmosphere was exchanged with 02, and the reaction was stirred under an 02 balloon for 6 h. Additional <strong>[99769-19-4](3-(methoxycarbonyl)phenyl)boronic acid</strong> (3.22 g, 17.9 mmol), pyridine (1.45 mL, 17.9 mmol) and 4A molecular sieves (1.7 g) were added. The reaction mixture was stirred atroom temperature overnight. Additional <strong>[99769-19-4](3-(methoxycarbonyl)phenyl)boronic acid</strong> (3.22 g, 17.9 mmol), pyridine (1.45 mL, 17.9 mmol) and Cu(OAc)2 (400 mg)were added to the reaction. After stirring at room temperature for 7 h, the reaction mixture was filtered through Celite rinsing with CHC13. The filtrate was diluted with water and ammonium hydroxide (18.6 mL, 143 mmol) was added. The aqueous layer was extracted with CHC13and the combined organic layers were washed with 10% LiC1. The organic layer was concentrated and purified by silica gel chromatography (220 g column, gradient from 0% to 50%EtOAc/CH2C12). The fractions were concentrated in vacuo until a white precipitate formed which collected via filtration and rinsed with EtOAc to give the title compound (1.33 g, 57%) as a white solid. ?H NMR (400 MHz, CDC13) oe 7.94 (t, J=1 .8Hz, 1H), 7.85 (d, J=2. 1 Hz, 1H), 7.82 (dt, J=7.7, 1.3 Hz, 1H), 7.48 (t, J7.9 Hz, 1H), 7.40(d, J2.1 Hz, 1H), 7.36 (ddd, J8.0, 2.3, 1.0 Hz, 1H), 6.32 (s, 1H), 3.94 (s, 3H), 2.45 (s,3H), 2.29 (s, 3H); LCMS (M+H) = 358.2; HPLC RT = 2.70 mm (Column: ChromolithODS S5 4.6 x 50 mm; Mobile Phase A: 10:90 MeOH:water with 0.1% TFA; MobilePhase B: 90:10 MeOH:water with 0.1% TFA; Temperature: 40C; Gradient: 0-100% Bover 4 mm; Flow: 4 mL/min).
57%	With pyridine; copper diacetate; In chloroform; at 20℃; for 6h;Molecular sieve; Inert atmosphere;	To a 250 mL round bottom flask containing 2-chloro-5-(3,5-dimethylisoxazol-4-yl)pyridin-3-amine (2.0 g, 8.9 mmol), <strong>[99769-19-4](3-(methoxycarbonyl)phenyl)boronic acid</strong> (Aldrich, 3.22 g, 17.9 mmol), Cu(OAc)2 (2.43 g, 13.4 mmol) and powdered 4 molecular sieves (7.0 g) was added CHCl3 (50 mL) and pyridine (1.45 mL, 17.9 mL). The atmosphere was exchanged with O2, and the reaction was stirred under an O2 balloon for 6 h. Additional <strong>[99769-19-4](3-(methoxycarbonyl)phenyl)boronic acid</strong> (3.22 g, 17.9 mmol), pyridine (1.45 mL, 17.9 mmol) and 4 molecular sieves (1.7 g) were added. The reaction mixture was stirred at room temperature overnight. Additional <strong>[99769-19-4](3-(methoxycarbonyl)phenyl)boronic acid</strong> (3.22 g, 17.9 mmol), pyridine (1.45 mL, 17.9 mmol) and Cu(OAc)2 (400 mg) were added to the reaction. After stirring at room temperature for 7 h, the reaction mixture was filtered through Celite rinsing with CHCl3. The filtrate was diluted with water and ammonium hydroxide (18.6 mL, 143 mmol) was added. The aqueous layer was extracted with CHCl3 and the combined organic layers were washed with 10% LiCl. The organic layer was concentrated and purified by silica gel chromatography (220 g column, gradient from 0% to 50% EtOAc/CH2Cl2). The fractions were concentrated in vacuo until a white precipitate formed which collected via filtration and rinsed with EtOAc to give the title compound (1.33 g, 57%) as a white solid. 1H NMR (400 MHz, CDCl3) delta 7.94 (t, J=1.8 Hz, 1H), 7.85 (d, J=2.1 Hz, 1H), 7.82 (dt, J=7.7, 1.3 Hz, 1H), 7.48 (t, J=7.9 Hz, 1H), 7.40 (d, J=2.1 Hz, 1H), 7.36 (ddd, J=8.0, 2.3, 1.0 Hz, 1H), 6.32 (s, 1H), 3.94 (s, 3H), 2.45 (s, 3H), 2.29 (s, 3H); LCMS (M+H)=358.2; HPLC RT=2.70 min (Column: Chromolith ODS S5 4.6×50 mm; Mobile Phase A: 10:90 MeOH:water with 0.1% TFA; Mobile Phase B: 90:10 MeOH:water with 0.1% TFA; Temperature: 40 C.; Gradient: 0-100% B over 4 min; Flow: 4 mL/min).
56.2%	With pyridine; oxygen; palladium diacetate; In chloroform; at 20℃; for 40h;	The racemate of the methyl ester of the title compound was prepared according the literature using the scheme described above (US 2016/0176864). [00237] Methyl 3-(3,5-dimethylisoxazol-4-yl)-5-(phenyl(tetrahydro-2H-pyran-4-yl)methyl)- 5H-pyrido[3,2-b]indole-7-carboxylate (0.22 g, prepared according to literature and the synthetic route above) was separated by chiral HPLC to give (R)-methyl 3-(3,5- dimethylisoxazol-4-yl)-5-(phenyl(tetrahydro-2H-pyran-4-yl)methyl)-5H-pyrido[3,2-b]indole-7- carboxylate (0.095 g) and (S)-methyl 3-(3,5-dimethylisoxazol-4-yl)-5-(phenyl(tetrahydro-2H- pyran-4-yl)methyl)-5H-pyrido[3,2-b]indole-7-carboxylate (0.090 g) as a yellow solid. H NMR (racemate) (400 MHz, CDC13) delta 0.98-1.02 (IH, m), 1.32-1.36 (2H, m), 1.95 (IH, s), 2.15 (3H, s), 2.31 (3H, s), 3.00-3.08 (IH, m), 3.24-3.31 (IH, m), 3.45-3.51 (IH, m), 3.76-3.80 (IH, m), 3.96 (3H, s), 4.00-4.01 (IH, m), 5.52 (IH, d, J = 10.8 Hz), 7.22-7.29 (3H, m), 7.38-7.40 (2H, m), 7.51 (IH, d, J = 1.6 Hz), 7.99 (IH, dd, / = 8.0, 1.2 Hz), 8.36 (IH, d, J = 8.0 Hz), 8.39 (2H, s); LC/MS 496.3 [M+H]+. [00238] The chiral material ester was hydrolyzed under basic condition (aq. NaOH in MeOH) to provide (R)-PTM-3-l-A and (S)-PTM-3-l-B.

Reference： [1]Patent: WO2015/100282,2015,A1 .Location in patent: Page/Page column 67
[2]Patent: US2016/176864,2016,A1 .Location in patent: Paragraph 0344
[3]Patent: WO2017/30814,2017,A1 .Location in patent: Paragraph 00236-00237

64
[ 2441-97-6 ]
[ 99769-19-4 ]
(-)-(S)-3-(3-methoxycarbonylphenyl)cyclohexene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With [Rh(OH)(cod)]2; 2,2',6,6'-tetramethoxy-4,4'-bis(di(3,5-dimethylphenyl)phosphino)-3,3'-bipyridine; caesium carbonate; In tetrahydrofuran; at 60℃; for 1h;	General procedure: General procedure for the AAA of allyl chlorides with boronic acids, [Rh(cod)(OH)]2 (4.6 mg, 0.01 mmol, 0.025 equiv.), A (18.2 mg, 0.024 mmol, 0.06 equiv.) and Cs2CO3 (130.3 mg, 0.40 mmol, 1.00 equiv.) were stirred in THF (2 ml) in a 10 ml round-bottomed flask at 60 C for 30 minutes. A solution of the boronic acid (0.80 mmol, 2.00 equiv.) and the allyl chloride (0.40 mmol, 1.00 equiv.) in THF (1.5 ml) was then added via syringe and the flask rinsed with THF (0.5 ml). The resulting mixture was stirred for one hour at 60 C before the addition of SiO2 (20 mg). The solvent was then evaporated carefully and the solid loaded directly onto a flash chromatography column to obtain the purified product.
86%	With hydroxy(1,5-cyclooctadiene)rhodium(I) dimer; caesium carbonate; (S)-2,2',6,6'-tetramethoxy-4,4'-bis(di(3,5-xylyl)phosphino)-3,3'-bipyridine; In tetrahydrofuran; at 60℃; for 1h;	[00109] In a 10 mL round bottomed flask [Rh(cod)(OH)]2 (4.6 mg, 0.01 mmol, 0.025 eq), (S)Xyl-P-PHOS A (18.2 mg, 0.024 mmol, 0.06 eq) and 0S2003 (130.3 mg, 0.40 mmol, 1 .00 eq) were stirred in THF (2 mL) at 60 C for 30 mm. A solution of 3-methoxycarbonylphenylboronic acid (144.0 mg, 0.80 mmol, 2.00 eq) and 3-chlorocyclohexene (45 jiL, 0.40 mmol, 1.00 eq) in THF (1.5 mL) was then added via syringe and the flask rinsed with THF (0.5 mL). The resulting mixture was then stirred for 1 h at 60 C before the addition of Si02 (20 mg). The solvent was then carefully evaporated and the solid directly loaded onto the top of a flash chromatography column. The column was eluted with hexane:EtOAc (92:8) to obtain the pure product in 86% yield (74.0 mg, 0.34 mmol) as a colorless oil.Enantiomeric excess of 99.9% was determined by HPLC [Chiralpak ID; flow: 1 .0 mL/min; hexane:IPA 99:1 100; A = 210 nm; major enantiomer tp = 5.6 mm; minor enantiomer tp = 6.1 mini.1H NMR (400 MHz, CDCI3) OH /ppm: 7.93 - 7.84 (m, 2H), 7.47 - 7.32 (m, 2H), 5.98 - 5.88 (m,1H), 5.70 (m, 1H), 3.91 (5, 3H), 3.46 (m, 1H), 2.10 (m, 2H), 2.06-1.97 (m, 1H), 1.81 -1.48(m, 3H).13C NMR (101 MHz, CDCI3) Oc/ppm: 167.5, 147.2, 132.6, 130.3, 129.6, 129.1, 129.0, 128.4,127.4, 5.20, 41.8, 32.7, 25.1, 21.2.HRMS (El/Fl) m/z calcd for C14H1602 [M]: 216.1150, found: 216.1148.IR (ATR) v (cm1, CHCI3): 3020, 2930, 2857, 1721.[a]2 589 = -101 .0 (c 1.12 CHCI3) for 99.9% ee.

Reference： [1]Nature Chemistry,2015,vol. 7,p. 935 - 939
[2]Patent: WO2016/198836,2016,A1 .Location in patent: Paragraph 00109

65
[ 7321-55-3 ]
[ 99769-19-4 ]
[ 13531-48-1 ]

Reference： [1]Angewandte Chemie - International Edition,2016,vol. 55,p. 326 - 330
Angew. Chem.,2016,vol. 128,p. 334 - 338

66
[ 5751-51-9 ]
[ 99769-19-4 ]
(R)-methyl 3-(7-methyl-4-oxochroman-2-yl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%		Example 18B (i?)-methyl 3 -(7-methyl-4-oxochroman-2-yl)benzoate A 20mL vial was charged with bis(2,2,2-trifluoroacetoxy)palladium (0.353 g, 1.061 mmol), (5)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole (0.260 g, 1.274 mmol), ammonium hexafluorophosphate(V) (1.038 g, 6.37 mmol) and (3-(methoxycarbonyl) phenyl) boronic acid (3.82 g, 21.23 mmol) were stirred in dichloroethane (10 mL) at room temperature for 5 minutes. To this suspension was added Example 18A (1.70 g, 10.61 mmol) and water (0.256 mL, 14.19 mmol). The vial was capped and the mixture was stirred at 60 C overnight. The mixture was filtered through a plug of celite and eluted with ethyl acetate. The solvent was removed under pressure and the crude material was chromatographed using a 80 g silica gel cartridge, eluting with a gradient of 5-50 % ethyl acetate in heptane to provide the title compound (2.6 g, 83 % yield). 1H NMR (400 MHz, CDC13) delta 8.22 - 8.13 (m, 1H), 8.11 - 8.01 (m, 1H), 7.83 (d, J= 8.3 Hz, 1H), 7.77 - 7.60 (m, 1H), 7.52 (t, J= 7.7 Hz, 1H), 6.89 (d, J= 6.8 Hz, 2H), 5.51 (dd, J = 13.2, 2.9 Hz, 1H), 4.13 (s, OH), 3.95 (d, J= 1.0 Hz, 3H), 3.76 (s, OH), 3.05 (ddd, J= 16.8, 13.3, 1.0 Hz, 1H), 2.88 (ddd, J= 16.8, 2.9, 0.9 Hz, 1H), 2.38 (s, 3H); MS (ESI+) m/z 297 (M+H)+.

Reference： [1]Patent: WO2016/69757,2016,A1 .Location in patent: Page/Page column 138-139
[2]Journal of Medicinal Chemistry,2018,vol. 61,p. 1436 - 1449

67
[ 80058-84-0 ]
[ 99769-19-4 ]
methyl 4'-amino-3',5'-diisopropyl-[1,1'-biphenyl]-3-carboxylate [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2016,vol. 55,p. 11907 - 11911
Angew. Chem.,2016,vol. 128,p. 12086 - 12090,5

68
[ 626-39-1 ]
[ 99769-19-4 ]
[ 118688-54-3 ]

Yield	Reaction Conditions	Operation in experiment
88%		H3BTMB was synthesized by the method described in Tetrahedron 66 (2010) 3553-3563. Specifically, a mixture containing 1,3,5-tribromobenzene (0.500 g), m-methoxycarbonyl phenylboronic acid (1.0560 g), K3PO4 (2.3586 g), and Pd(PPh3)4 (0.0550 g) was stirred in 1,4-dioxane (50 mL) in a nitrogen atmosphere at 90 C. for 3 days. The reaction mixture was cooled to room temperature, and the solvent was evaporated. The residue was dissolved in CH2Cl2, washed with water, and dried over MgSO4. The product was purified by silica gel column chromatography, which used CH2Cl2/n-hexane=(2:1Delta1:0) for elution, and the third main product was obtained. The obtained product was recrystallized with CH2Cl2/n-hexane. The recrystallized product was dissolved in 45 mL of MeOH, 25 mL of 6-N NaOH aqueous solution was added to the reaction mixture, and the mixture was refluxed at 95 C. overnight. The reaction mixture was cooled to room temperature, 20 mL of concentrated HCl was added thereto, and the mixture was stirred for 1 hour. The white precipitate was filtered and vacuum-dried, thereby obtaining H3BTMB with a yield of 88%. FIG. 1a) shows the single crystal X-ray structure of the resulting H3BTMB. In the following Examples, anions derived from H3BTMB are noted as BTMB or BTMB3-.

Reference： [1]Patent: US2016/362359,2016,A1 .Location in patent: Paragraph 0094; 0095

69
[ 109745-70-2 ]
[ 99769-19-4 ]
[ 947590-66-1 ]

Yield	Reaction Conditions	Operation in experiment
88%	With potassium phosphate; di-mu-chloro-bis{2-[3-(2,6-diisopropylphenyl)imidazolin-2-ylidene]phenyl-kappa2C,C'}dipalladium(II); In toluene; at 70℃; for 2h;Sealed tube;	Using 3-(methoxycarbonyl)phenylboronic Acid 3k 0.090 g (0.5 mmol), Pd-catalyst 1a 0.0011 g (0.5 mol%Pd, 0.0025 mol), potassium phosphate 0.212 g (1.0 mmol) and methyl 2-hydroxy-2-methoxyacetate 2 0.181 g (1.5 mmol), the product was obtained in 88% (0.0983 g) yield as a white solid. IR (KBr, cm-1) 3427, 2958, 2362, 2073, 1981, 1928, 1730, 1587, 1435, 1282, 1196, 1105, 825; 1H NMR (300 MHz, CDCl3, ppm): 8.13 (1H, s), 8.02 (1H, ddd, J = 1.4, 1.4, 7.8 Hz), 7.65 (1H, ddd, J = 1.4, 1.4, 7.8 Hz), 7.47 (1H, dd, J = 7.8, 7.8 Hz), 5.26 (1H, d, J = 5.3 Hz), 3.94 (3H, s,), 3.79 (3H, s), 3.58 (1H, d, J = 5.3 Hz); 13C NMR (75 MHz, CDCl3, ppm): 173.7, 166.7, 138.7, 131.0, 130.6, 129.7, 128.7, 127.8, 72.4, 53.2, 53.2; HRMS (FAB) m/z: [M+H]+ calcd. for C11H12O6: 225.0763. Found: 225.0766.

Reference： [1]Tetrahedron Letters,2017,vol. 58,p. 2495 - 2497

70
[ 1127-76-0 ]
[ 99769-19-4 ]
C₂₀H₁₈O₂ [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2017,vol. 139,p. 7709 - 7712

71
[ 5707-44-8 ]
[ 99769-19-4 ]
C₂₂H₂₀O₂ [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2017,vol. 139,p. 7709 - 7712

72
[ 99769-19-4 ]
[ 175205-82-0 ]
C₁₄H₁₀F₃NO₂ [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2017,vol. 27,p. 3817 - 3824

73
[ 99769-19-4 ]
5-bromo-10,20-bis(3,5-di-tert-butylphenyl)-21H,23H-porphine [ No CAS ]
10,20-bis(3,5-di-tert-butyl)phenyl-5-(3’-carboxymethyl)phenylporphyrin [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 66℃; for 16h;Inert atmosphere;	Porphyrin 4a (300 mg,0.39 mmol) was dissolved in THF (20 mL). The solution was then degased via three freeze-pump-thawcycles and the flask was purged with argon. 3-Methoxycarbonylphenylboronic acid (282 mg, 1.57 mmol),Pd(PPh3)4 (68 mg, 0.06 mmol) and K3PO4 (831 mg, 3.92 mmol) were added. The mixture was stirred at66 C for 16 h. The solvent was removed in vacuo and the crude product was washed with NaHCO3 andH2O. The solvent was removed and the residue was dissolved in CH2Cl2 and filtered through silica gel.The porphyrin was purified with column chromatography using CH2Cl2:petroleum ether (1:1). The targetwas obtained in 90% yield (291 mg, 0.35 mmol) after recrystallization from CH2Cl2: MeOH

Reference： [1]Heterocycles,2017,vol. 94,p. 1518 - 1541

74
[ 914612-23-0 ]
[ 99769-19-4 ]
methyl 3-(6-benzyl-5,6,7,8-tetrahydropyrido[4,3-d]pyrimidin-4-yl)benzoate [ No CAS ]

Reference： [1]ACS Medicinal Chemistry Letters,2017,vol. 8,p. 975 - 980

75
[ 89599-01-9 ]
[ 99769-19-4 ]
C₃₆H₄₀N₂O₆S [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry,2017,vol. 25,p. 5569 - 5575

76
[ 89599-01-9 ]
[ 99769-19-4 ]
3'-sulfamoyl[1,1'-biphenyl]-3-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; at 110℃; for 3h;	General procedure: a two-necked round bottom flask was charged with <strong>[89599-01-9]3-bromobenzenesulfonamide</strong> (0.24g, 1 mmol), 3-boronobenzoic acid 1-methyl ester (216 mg, 1.2 mmol), [1,1?-bis(diphenylphosphino)ferrocene]dichloropalladium (II), DCM complex (36 mg, 0.05 mmol), and potassium carbonate (207 mg, 1.5 mmol). The solids were purged with nitrogen for about ten minutes, then 1,4-dioxanes (5 ml) and water (0.25 ml) was added, and nitrogen bubbled through for about ten minutes. Then the mixture was heated and allowed to reflux (about one to two hours was required for complete consumption of aryl bromide). The crude was then subjected to MPLC (in this case, 0 to 60% ethyl acetate in hexanes) to afford 234 mg of material (80%). The ester was then hydrolyzed using ten equivalents of 5 M NaOH in THF, which required two hours of stirring for complete hydrolysis, yields are typically between 90 and 99% following removal of THF, acidification with HCl (resulting in a solid which can be collected), and drying: 1H NMR (300 MHz, DMSO-d6)d 8.25 (bs, 1H), 8.15 (bs, 1H), 8.02 - 7.95 (m, 3H), 7.86 - 7.83 (m, 1H), 7.68 (q, J = 7.8 Hz, 2H), 7.45 (s, 2H).

Reference： [1]Bioorganic and Medicinal Chemistry,2017,vol. 25,p. 5569 - 5575

77
[ 1035235-27-8 ]
[ 99769-19-4 ]
tert-butyl 4-(3-(methoxycarbonyl)phenyl)isoindoline-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
0.33 g	With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In 1,4-dioxane; water; at 80℃; for 24.0h;Inert atmosphere;	Step a. To a stirred solution of <strong>[1035235-27-8]tert-butyl 4-bromoisoindoline-2-carboxylate</strong> (Intermediate 1, 0.35 g, 1.185 mmol) in 1,4-dioxane: water (4: 1; 20 ml) was added Cs2C03 (0.77 g, 2.371 mmol) at rt under nitrogen. The reaction was purged with nitrogen for 15 min. Pd(PPh3)4 (0.14 g, 0.118 mmol) was added to the reaction mixture and purged with nitrogen for 10 min. 3- (Methoxycarbonyl)phenylboronic acid (CAS Number 99769-19-4; available from Combi Blocks) (0.26 g, 1.422 mmol) was added to the reaction mixture. The reaction mixture was heated at 80C for 24 h. The resulting reaction mixture was cooled to rt, poured into water (20 ml) and extracted with EtOAc (3 x 50). The combined organic phase was washed with brine (80 ml). The organic phase was separated, dried over Na2S04, filtered and concentrated under reduced pressure. The resulting crude material was purified by flash chromatography (5% EtOAc in hexane) yielding tert-butyl 4-(3- (methoxycarbonyl)phenyl)isoindoline-2-carboxylate (0.33 g, 0.932 mmol). LCMS: Method A, 2.782 min, MS: ES+ 298.4 (M-56); 1H NMR (400 MHz, CDC13) delta ppm 8.04 - 8.11 (m, 2 H), 7.62 (d, J=7.2 Hz, 1H), 7.49 - 7.58 (m, 2 H), 7.40 (t, J=7.2 Hz, 1H), 7.31 - 7.33 (m, 1H), 4.69 - 4.79 (m, 4 H), 3.95 (s, 3 H), 1.53 (s, 9 H).

Reference： [1]Patent: WO2017/158388,2017,A1 .Location in patent: Page/Page column 99

78
[ 1017781-60-0 ]
[ 99769-19-4 ]
C₁₅H₁₆N₂O₃S [ No CAS ]

Reference： [1]Chemical Biology and Drug Design,2018,vol. 91,p. 172 - 180

79
[ 676448-17-2 ]
[ 99769-19-4 ]
C₂₁H₂₁NO₄ [ No CAS ]

Reference： [1]ChemCatChem,2018,vol. 10,p. 601 - 611

80
[ 99769-19-4 ]
[ 171663-13-1 ]
[ 478374-95-7 ]

Reference： [1]ACS Medicinal Chemistry Letters,2018,vol. 9,p. 490 - 495

81
[ 2255-80-3 ]
[ 99769-19-4 ]
4-methyl-7-(2-acetoxy-5-methoxycarbonylphenyl)-2,1,3-benzothiadiazole [ No CAS ]

Reference： [1]Organic Letters,2018,vol. 20,p. 5692 - 5695

82
[ 2255-80-3 ]
[ 99769-19-4 ]
C₁₅H₁₂N₂O₂S [ No CAS ]

Reference： [1]Organic Letters,2018,vol. 20,p. 5692 - 5695

83
[ 1483-55-2 ]
[ 99769-19-4 ]
methyl 2'-cyano-4'-(trifluoromethyl)-[1,1'-biphenyl]-3-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92.9%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate; at 80℃; for 2h;Sealed tube; Inert atmosphere;	A microwave reaction vessel was charged with (3-(methoxycarbonyl)phenyl)boronic acid(540 mg, 3 mmol), <strong>[1483-55-2]2-bromo-5-(trifluoromethyl)benzonitrile</strong> (500 mg, 2 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (82 mg, 0.2 mmol), potassium phosphate tribasic (1.27 g, 6 mmol) and palladium(II) acetate (22.5 mg, 0.1 mmol) and was sealed. It was put under vacuum and filled with argon (3x repeated). Then the degassed toluene was added and the suspension was stirred at 80C for 2 hours. The reaction mixture was then allowed to cool to room temperature, diluted with 5 ml EtOAc and filtered through a thin bed of silica (0.3-0.5 mm) and eluted/washed with EtOAc (ca. 40 ml) and concentrated under reduced pressure. After Si02 flash chromatography, methyl 2'-cyano-4'-(trifluoromethyl)-[1,1'-biphenyl]-3-carboxylate was obtained as a off-white, crystalline solid (567 mg, 92.9%). MS (ESI): m/z = 306.2 [M+H]+.

Reference： [1]Patent: WO2018/189063,2018,A1 .Location in patent: Paragraph 32

84
[ 99769-19-4 ]
[ 263159-64-4 ]
methyl 2'-cyano-6'-methyl-[1,1'-biphenyl]-3-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97.3%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate; In toluene; at 80℃; for 2h;Inert atmosphere;	A microwave reaction vessel was charged with (3-(methoxycarbonyl)phenyl)boronic acid (540 mg, 3 mmol), <strong>[263159-64-4]2-bromo-3-methylbenzonitrile</strong> (392 mg, 2 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (82 mg, 0.2 mmol), potassium phosphate tribasic (1.27 g, 6 mmol), and palladium(II) acetate (22.5 mg, 0.1 mmol) and was sealed. It was put under vacuum and filled with argon (3x repeated). Then the degassed toluene was added and the suspension was stirred at 80C for 2 hours. The reaction mixture was then allowed to cool to room temperature, diluted with 5 ml EtOAc and filtered through a thin bed of silica (0.3-0.5 mm) and eluted/washed with EtOAc (ca. 40 ml) and concentrated under reduced pressure. After Si02 flash chromatography, methyl 2'-cyano-6'-methyl-[1,1'-biphenyl]-3-carboxylate was obtained as a off-white, crystalline solid (489 mg, 97.3%). MS (ESI): m/z = 252.2 [M+H]+.

Reference： [1]Patent: WO2018/189063,2018,A1 .Location in patent: Page/Page column 33; 34

85
[ 35764-15-9 ]
[ 99769-19-4 ]
methyl 3-[2-cyano-5-(trifluoromethyl)phenyl]benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73.8%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate; In water; toluene; at 6.0℃; for 110.0h;	To a solution of (3-(methoxycarbonyl)phenyl)boronic acid (324 mg, 1.8 mmol, Eq: 1.5) in toluene (5 mL) and water (500 muEpsilon) was added <strong>[35764-15-9]2-bromo-4-(trifluoromethyl)benzonitrile</strong> (300 mg, 1.2 mmol, Eq: 1) and SPhos (49.3 mg, 120 muiotaetaomicron, Eq: 0.1) and potassium phosphate tribasic anhydrous (764 mg, 3.6 mmol, Eq: 3) and palladium(II) acetate (13.5 mg, 60 muiotaetaomicron, Eq: 0.05). The reaction mixture was stirred for 6 hours at 110C.The reaction mixture was poured on 30 mL 10% aqueous NaHC03 solution and 30 mL EtOAc and the layers were separated. The aqueous layer was extracted a second time with 30 mL EtOAc. The organic layers were washed with 30 mL brine, dried over MgS04, filtered and concentrated under vacuum.The residue was purified by silica gel chromatography to yield methyl 3-[2-cyano-5-(trifluoromethyl)phenyl]benzoate (338 mg, 73.8%). GCMS (EI): m/z = 305.1 [M+H]+.

Reference： [1]Patent: WO2018/189063,2018,A1 .Location in patent: Page/Page column 40

86
[ 61326-44-1 ]
[ 99769-19-4 ]
C₅₈H₄₄O₈ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In ethanol; toluene; at 110℃; for 24h;Inert atmosphere;	4 g of 3-methoxycarbonylbenzene borate, 1 g of 4Br-TPE and 0.47 g of tetratriphenylphosphine The palladium was uniformly mixed, vacuumed for 5 min and nitrogen-filled for 5 min for 3 times. 100 mL of a toluene ethanol solution with a volume ratio of 9:1 and 12 mL of a 1 mol/L solution of tripotassium phosphate were injected and refluxed at 110 ° C for 24 h until the starting of the reaction. . The mixture was cooled to room temperature, filtered (dichloromethane), and the filtrate was evaporated to dryness.Finally, the column is treated to obtain pure 1,1,2,2-tetra[[3-benzomethoxycarbonyl)benzene]ethylene;

Reference： [1]Patent: CN109651126,2019,A .Location in patent: Paragraph 0006; 0019; 0022; 0025

87
[ 82632-80-2 ]
[ 99769-19-4 ]
methyl 3-{3,6,7,10,11-pentakis[3-(methoxycarbonyl)phenyl]triphenylen-2-yl}benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,4-dioxane; at 80℃; for 16h;Inert atmosphere;	3.69 g (5.25 mmol) of hexabromobenzophenanthrene, 8.51 g (47.3 mmol) of 4-methoxycarbonylbenzeneboronic acid,5.01 g (47.3 mmol) sodium carbonate, 0.60 g (0.517 mmol) tetrakistriphenylphosphine palladium,75mL 1,4-dioxane was added to a 500mL three-necked bottle, sealed, vacuumed, and protected by nitrogen.The reaction was carried out at 80 C for 16 hours. After the reaction stops,The crystals are allowed to stand, and dried by filtration to obtain 3,3',3",3"',3"",3""'-(triphenylene-2,3,6,7,10,11-hexa)hexabenzene Formate 4.7 g, yield 81%.

Reference： [1]Patent: CN109836326,2019,A .Location in patent: Paragraph 0019; 0025-0026

88
[ 13195-50-1 ]
[ 99769-19-4 ]
methyl-3-(5-nitrothiophen-2-yl)benzoate [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2019

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H420	Harms public health and the environment by destroying ozone in the upper atmosphere

[ CAS No. 99769-19-4 ] {[proInfo.proName]}

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[ 99769-19-4 ] Synthesis Path-Upstream 1~10

[ 99769-19-4 ] Synthesis Path-Downstream 1~88

Related Functional Groups of [ 99769-19-4 ]

Organoboron

Aryls

Esters

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[ 99769-19-4 ]