[ CAS No. 87199-15-3 ]

Name: 87199-15-3|3-(Hydroxymethyl)phenylboronic acid|98%
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Quality Control of [ 87199-15-3 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 87199-15-3 ]

SDS Specification

Alternatived Products of [ 87199-15-3 ]

Product Details of [ 87199-15-3 ]

CAS No. :	87199-15-3	MDL No. :	MFCD01317846
Formula :	C₇H₉BO₃	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	HGTDLKXUWVKLQX-UHFFFAOYSA-N
M.W :	151.96	Pubchem ID :	2734662
Synonyms :

Calculated chemistry of [ 87199-15-3 ]

Physicochemical Properties

Num. heavy atoms :	11
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.14
Num. rotatable bonds :	2
Num. H-bond acceptors :	3.0
Num. H-bond donors :	3.0
Molar Refractivity :	42.4
TPSA :	60.69 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 :	Yes
Log Kp (skin permeation) :	-7.27 cm/s

Lipophilicity

Log Po/w (iLOGP) :	0.0
Log Po/w (XLOGP3) :	-0.06
Log Po/w (WLOGP) :	-1.29
Log Po/w (MLOGP) :	-0.27
Log Po/w (SILICOS-IT) :	-0.91
Consensus Log Po/w :	-0.51

Druglikeness

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

Water Solubility

Log S (ESOL) :	-1.02
Solubility :	14.6 mg/ml ; 0.0964 mol/l
Class :	Very soluble
Log S (Ali) :	-0.76
Solubility :	26.2 mg/ml ; 0.172 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-1.1
Solubility :	12.0 mg/ml ; 0.0793 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.58

Safety of [ 87199-15-3 ]

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 [ 87199-15-3 ]

* 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 [ 87199-15-3 ]
Downstream synthetic route of [ 87199-15-3 ]

[ 87199-15-3 ] Synthesis Path-Upstream 1~8

1
[ 87199-15-3 ]
[ 1877-77-6 ]

Reference： [1] Chemistry - A European Journal, 2011, vol. 17, # 20, p. 5652 - 5660

2
[ 5419-55-6 ]
[ 103978-12-7 ]
[ 87199-15-3 ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: With n-butyllithium In tetrahydrofuran at -78℃; for 0.5 h; Stage #2: at 20℃; for 2.83 h;	Example 3B: 3 -(Hydroxymethyl)phenylboronic acid j00214j Example 3A (150 mg, 0.49 8 mmol) was dissolved in THF (2.49 mL) and cooled to -78 °C. BuLi (431 .iL, 0.647 mmol) was and the reaction was stirred for 30 mm. After this time, triisopropyl borate (231 jiL, 0.996 mmol) was added and stirring continued for 20 mm, then the reaction was warmed to ambient temperature and allowed to stir for 2.5 h. The reaction mixture was diluted with EtOAc and washed with water,then brine, dried (Na2SO4), filtered, and concentrated in vacuo. The crude material was then dissolved in HPLC solvent B (90:10:0.1 MeCN:H20:TFA) and allowed to stir at ambient temperature for 1 h. The reaction was concentrated in vacuo and the crude material was purified by Prep LC (Axia Luna 5t C18 30x100 mm column, 10 mm gradient from 20 to 100percent B in A, A = 10:90:0.1 MeCN:H20:TFA, B = 90:10:0.1MeCN:H20:TFA) to yield Example 3B (57 mg, 75percent). 1H NMR (400 MHz, ACETONITRILE-d3) ö ppm 7.75 (1 H, s), 7.67 (1 H, d, J=7.28 Hz), 7.40 - 7.48 (1 H, m), 7.30 - 7.40 (1 H, m), 4.60 (2 H, s).

Reference： [1] Patent: WO2014/201073, 2014, A1, . Location in patent: Paragraph 00214
[2] ACS Medicinal Chemistry Letters, 2017, vol. 8, # 1, p. 67 - 72

3
[ 109-72-8 ]
[ 121-43-7 ]
[ 15852-73-0 ]
[ 87199-15-3 ]

Yield	Reaction Conditions	Operation in experiment
98%	With hydrogenchloride In tetrahydrofuran; hexane	Part A 3-Bromobenzyl alcohol (2.0 g, 10.7 mmol) was dissolved in dry THF (50 ml) in a dry 100 ml flask flushed with nitrogen. The mixture was chilled in a dry ice/acetone bath. n-Butyl lithium (11 ml of a 2.13M solution in hexane, 23.5 mmol) was added. The reaction was warmed to room temperature for 1 hour, then cooled in an ice water bath. Trimethyl borate (1.3 ml, 11.2 mmol) was added and the mixture was stirred at room temperature overnight, then treated with 2N aqueous HCl to pH 2, and stirred for 3 hours. Brine (15 ml) was added, and the mixture was extracted with ethyl acetate (3*15 ml). The organic materials were combined, dried (MgSO₄) then concentrated under reduced pressure which gave of 3-hydroxymethylbenzeneboronic acid (98percent) as a clear oil.

Reference： [1] Patent: US5444050, 1995, A,

4
[ 15852-73-0 ]
[ 87199-15-3 ]

Reference： [1] Patent: WO2014/201073, 2014, A1,
[2] ACS Medicinal Chemistry Letters, 2017, vol. 8, # 1, p. 67 - 72

5
[ 5419-55-6 ]
[ 15852-73-0 ]
[ 87199-15-3 ]

Reference： [1] Organic Process Research and Development, 2018, vol. 22, # 6, p. 741 - 746

6
[ 87199-15-3 ]
[ 364794-80-9 ]

Reference： [1] Organic Letters, 2013, vol. 15, # 18, p. 4850 - 4853

7
[ 87199-15-3 ]
[ 883738-27-0 ]

Reference： [1] Organic Letters, 2013, vol. 15, # 18, p. 4850 - 4853

8
[ 76-09-5 ]
[ 87199-15-3 ]
[ 443776-76-9 ]

Reference： [1] Organic Letters, 2013, vol. 15, # 18, p. 4850 - 4853

[ 87199-15-3 ] Synthesis Path-Downstream 1~68

1
[ 87199-15-3 ]
[ 342777-09-7 ]
[ 939-57-1 ]
(E)-3-[2-(3-Hydroxymethyl-benzyl)-phenyl]-acrylic acid [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2001,vol. 11,p. 747 - 749

2
[ 69038-74-0 ]
[ 87199-15-3 ]
[ 901300-63-8 ]

Reference： [1]Synlett,2006,p. 865 - 868

3
[ 104-21-2 ]
[ 87199-15-3 ]
{3-(4-methoxybenzyl)phenyl}methanol [ No CAS ]

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

4
[ 862730-04-9 ]
[ 87199-15-3 ]
(3-(4-amino-1-isopropyl-1H-pyrazolo[3,4-d]pyrimidin-3-yl)phenyl)methanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
42%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; ethanol; water; at 80℃;	Synthesis of (3-(4-amino-1-isopropyl-1H-pyrazolo[3,4-d]pyrimidin-3-yl)phenyl)methanol (BA26); A solution of (3-Hydroxymethylphenyl)boronic acid (24 mg, 0.13 mmol) in EtOH (3.3 ml) was added to a solution of <strong>[862730-04-9]3-iodo-1-isopropyl-1H-pyrazolo[3,4-d]pyrimidin-4-amine</strong> (20 mg, 0.07 mmol) in DME (12 ml). Pd(PPh3)4 (16 mg, 0.014 mmol) and saturated Na2CO3 (1.9 ml) were added and the reaction was heated to 80 C. under an argon atmosphere overnight. After cooling, the reaction was extracted with saturated NaCl and CH2Cl2. Organic phases were combined, concentrated in vacuo and purified by RP-HPLC (MeCN:H2O:0.1% TFA) to yield BA26 (8.4 mg, 42% yield). ESI-MS (M+H)+ m/z calcd 283.1, found 284.2.

Reference： [1]Patent: US2007/293516,2007,A1 .Location in patent: Page/Page column 13-14; 17

5
[ 1013098-89-9 ]
[ 87199-15-3 ]
[ 1013099-23-4 ]

Yield	Reaction Conditions	Operation in experiment
81.24%	With sodium hydrogencarbonate;tetrakis(triphenylphosphine) palladium(0); In methanol; toluene; at 100℃;	Example 35. 8-Cvclopentyl-6-(3-(hvdroxymethyl)phenyl)-4-nnethyl-2-(methylamino)pyridof2.3-dlpyrimidin- 7(8H)-one (Compound 148); 6-Bromo-8-cyclopentyl-4-methyl-2-methylamino-8H-pyrido[2,3-d]pyrimidin-7-one (5.00 g, 14.83 mmol), 3-(hydroxymethyl)phenylboronic acid (3.38 g, 22.24 mmol) and Pd(PPh3)4 (0.685 g, 0.593 mmol) were suspended in Toluene (20 mL), MeOH (10 ml.) and sat. NaHCO3 (10 mL) and then heated to 100 0C overnight. The reaction was deemed complete by MS and TLC. The organic layer was injected directly onto a column, eluting with CH2CI2 then 4 % MeOH in CH2CI2. The fractions containing the desired material, as deemed by MS, were combined and evaporated in vacuo to give a greenish beige solid. This was triturated with MeCN and filtered to give crop one, 4.7 g. A second crop was obtained of 0.25 g. A third crop was obtained of 0.10 g. The three crops were deemed to be of sufficient purity based on NMFTs and were combined and washed again with MeCN to give a solid (4.39 g, 81.24 %). Elemental Analysis: Calcd for C21H24N4O2, C 69.21 / 69.00, H 6.64 / 6.65, N 15.37 / 15.16. LRMS (M + H) +: 365.1 1H NMR (CDCI3, 400 MHz): 7.73 (1 H, s) 7.61 (1 H, s), 7.53 (1 H, d, J = 7.57 Hz), 7.40 (1 H, t, J = 7.69 Hz), 7.34 (1 H, d, J = 7.57 Hz), 6.04 (1 H, m), 5.27 (1 H, s), 4.74 (2 H, d, J = 6.11 Hz), 3.06 (3 H, d, J = 5.13 Hz), 2.56 (3 H, s), 2.40 (2 H, m), 2.05 (2 H, m), 1.66 (2 H, m).

Reference： [1]Patent: WO2008/32162,2008,A1 .Location in patent: Page/Page column 51

6
[ 5798-75-4 ]
[ 87199-15-3 ]
[ 579512-25-7 ]

Yield	Reaction Conditions	Operation in experiment
98%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 80℃; for 2h;	Example 3a3' -hydroxymethyl-biphenyl-4-carboxylic acid ethyl esterA solution of 4-bromo-benzoic acid ethyl ester (7.0 g, 30.5 mmol), 3- (hydroxymethyl) phenyl boronic acid (5.1 g, 33.6 iranol), and tetrakistriphenylphosphine palladium (Pd (PPh3) 4)(1.1 g, 0.91 mmol) in 75 mL of toluene and 75 mL ethanol (0.2M) is treated with 2M Na2CO3 (45.8 mL, 91.7 mmol). The reaction mixture is heated to 80 0C for 2 hours, cooled to room temperature, and diluted with ethyl acetate (200 mL) . The organic layer is extracted, dried over MgSO4, and concentrated. Purification by flash chromatography (20-30% ethyl acetate in heptane) affords 3' -hydroxymethyl-biphenyl-4-carboxylic acid ethyl ester (7.7 g, 98%) as a light yellow solid. 1H NMR (CDCl3, 300 MHz) delta 8.08 (d, J = 8.3 Hz, 2 H), 7.64 (d, J = 8.3 Hz, 2 H), 7.61 (s, 1 H), 7.53 (d, J = 7.4 Hz, 1 H), 7.44 (t, J = 7.4 Hz, 1 H), 7.38 (d, J = 7.4 Hz, 1 H) 4.77 (s, 2 H), 4.38 (q, J= 7.1 Hz, 2 H), 1.41 (t, J= 7.1 Hz, 3 H)

Reference： [1]Patent: WO2008/33455,2008,A2 .Location in patent: Page/Page column 104

7
[ 103978-12-7 ]
[ 87199-15-3 ]
[ 1013909-07-3 ]

Yield	Reaction Conditions	Operation in experiment
87%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 90℃; for 8h;	Example 7b(3' - (tert-butyl-dimethyl-silanyloxymethyl) -biphenyl-3-yl] - methanolA solution of (3-bromo-benzyloxy) -tert-butyl-dimethyl-silane (10.0 g, 33.2 mmol) , 3- (hydroxymethyl) phenyl boronic acid (5.5 g, 36.5 mmol), and tetrakistriphenylphosphine palladium (Pd(Ph3J4) (1.0 g, 0.87 mmol) in DME (80 mL, 0.4M) is treated with 2M Na2CO3 (20 mL, 40 mmol) . The reaction mixture is heated to 90 0C for 8 hours, cooled to room temperature, and the organics are extracted with ethyl acetate (2 x 75 mL) . Purification by flash chromatography (25% ethyl acetate in heptane) affords (3' - ( tert-butyl-dimethyl-silanyloxymethyl) - biphenyl-3-yl] -methanol (9.5 g, 87%) as an orange oil. 1H NMR (CDCl3, 300 MHz) delta 7.58-7.29 (m, 8 H), 4.80 (s, 2 H), 4.76 (s, 2 H) , 0.96 (s, 9 H) , 0.12 (s, 6 H)

Reference： [1]Patent: WO2008/33455,2008,A2 .Location in patent: Page/Page column 113

8
[ 2252-44-0 ]
[ 87199-15-3 ]
[ 613239-71-7 ]

Yield	Reaction Conditions	Operation in experiment
		The title compound was prepared in the manner analogous to Example 3A using 3-hydroxymethylphenylboronic acid and <strong>[2252-44-0]1-bromo-3-trifluoromethoxy-benzene</strong>. MS m/z 251 (M-1).

Reference： [1]Patent: US2003/225158,2003,A1 .Location in patent: Page 31

9
[ 402-43-7 ]
[ 87199-15-3 ]
[ 126485-55-0 ]

Yield	Reaction Conditions	Operation in experiment
92%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium carbonate; In 1,2-dimethoxyethane; at 80℃; for 18h;Inert atmosphere; Sealed tube;	An oven-dried 100 mL round bottom flask equipped with a stir bar was charged with Pd(dppf)Cl2 (365.9 mg, 0.50 mmol, 5 mol%) and 3-hydroxymethylphenylboronic acid (1.90 g, 12.5 mmol, 1.25 equivalents). The flask was sealed with a septum and the gas was replaced with Ar, then DME (20 mL) was added. Na2CO3 (2.12 g, 20.0 mmol, 2.0 equivalents) was added under a stream of argon, and then 4-bromotrifluorotoluene (1.40 mL, 10.0 mmol, 1.0 equivalent) was added via a syringe. The vessel was heated to 80 C, then sealed with a yellow plastic lid, and the reaction mixture was stirred for 18 hours. The vessel was cooled to room temperature, the reaction mixture was poured into Et2O (200 mL), and the organic phase was washed with H2O (2 x 100 mL), a 10 wt% aqueous solution of LiCl (50 mL), and brine (50 mL) in this order. The organic phase was dried over MgSO4, filtered and concentrated.The residue was purified by silica gel column chromatography (hexane: EtOAc = 2: 1 to 1: 1), Intermediate H (2.32 g, 92%) was obtained as a viscous brown oil which solidified upon standing to give an off-white solid.
		The title compound was prepared in the manner analogous to Example 3A with 1-bromo-4-trifluoromethyl-benzene and 3-(hydroxymethyl)phenyl boronic acid. MS m/z 251 (M-1).

Reference： [1]Patent: CN110590767,2019,A .Location in patent: Paragraph 0054; 0056-0059
[2]Patent: US2003/225158,2003,A1 .Location in patent: Page 52

10
[ 550999-37-6 ]
[ 87199-15-3 ]
N-[(3R)-1-azabicyclo[2.2.2]oct-3-yl]-6-[3-(hydroxymethyl)phenyl]-1-benzofuran-2-carboxamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
54%	With sodium hydroxide;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In DMF (N,N-dimethyl-formamide); water; at 80 - 85℃; for 18h;	Eine Mischung aus 130 mg (0.86 mmol) 3-(Hydroxymethyl) phenylboronsaeure, 200 mg (0.57 mmol) N [ (3R)-1-Azabicyclo [2.2. 2] [OCT-3-YL]-6-BROM-1-BENZOFURAN-2-] carboxamid (Beispiel 2A), 1.72 mL (1.72 mmol) [1 N] Natronlauge, 40 mg (0. [ 06 MMOL) L, L'-BIS] (diphenylphosphino) ferrocenpalladium [(II)] chlorid und 2 mL DMF wird [18 H AUF 80-85C] erhitzt. Das Solvens wird unter reduziertem Druck ent- fernt. Das Rohprodukt wird ueber Kieselgel 60 [(MERCK,] Darmstadt ; Eluent : Dichlor- methan, Dichlormethan-Methanol 20 : 1, Dichlormethan-Methanol-Ammoniak [80] : 20 : 2) gereinigt. Das Solvens wird unter reduziertem Druck entfernt. Schliesslich werden letzte Loesungsmittelreste im Hochvakuum entfernt. Es werden 127 mg (54 [%] d. Th. ) der Titelverbindung isoliert. [IH-NMR] (200 MHz, [CDC13)] : [8] [= 7.] 86 (d, [1H),] 7.72-7. 28 (m, 7H), 6.77 (d, [1H),] 4.62 [(S, 2H),] 4.28-4. 12 (m, 1H), 3.56-3. 38 (m, 1H), 3.04-2. 78 (m, 4H), 2.75-2. 59 [(M,] 1H), 2.16-2. 02 (m, [1H),] 1. [93-1.] 66 (m, 3H), 1.66-1. 45 [(M,] 1H). HPLC (Methode [1)] : [RT =] 3.5 min. LC-MS [(METHODE 2)] : Rt [= 1.] 50 min. MS (ESIpos) : m/z = 377 (M+H) +.

Reference： [1]Patent: WO2003/104227,2003,A1 .Location in patent: Page 69

11
[ 676491-19-3 ]
[ 87199-15-3 ]
[ 676491-22-8 ]

Yield	Reaction Conditions	Operation in experiment
71%		[0600] To a mixture of 4-(1-iodo-1-phenyl-methylene)-piperidine-1-carboxylic acid tert-butyl ester (0.132 g, 0.33 mmol) and 3-hydroxymethylphenylboronic acid (0.050 g 0.33 mmol) in DME (3 mL) was added 2M sodium carbonate (0.65 mL, 1.30 mmol). The reaction vessel was then flushed with Ar for 10 minutes, Pd2 dba3 (0.015 g, 0.016 mmol) was added, the vessel was sealed and the mixture was heated at 90 C. for 16 h. The cooled mixture was filtered (0.45 cm syringe filter) and the filtrate was evaporated. The residue was purified by preparative HPLC to give the title compound (0.037 g, 71%) as a white solid: [0601] 1Hnmr (400 MHz, CDCl3) delta 7.70-7.26 (m, 3H), 7.22-7.20 (m, 2H), 7.11-7.04 (m, 4H), 4.64 (s, 2H), 3.44 (m, 4H), 2.30 (m, 4H), 1.57 (br s, 1H), 1.44 (s, 9H).

Reference： [1]Patent: US2004/63744,2004,A1 .Location in patent: Page/Page column 109

12
[ 763120-71-4 ]
[ 87199-15-3 ]
6-(3-hydroxymethyl-phenyl)-2H-[1,2,4]triazolo[4,3-a]quinolin-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75.5%	With caesium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 165℃; for 0.333333h;Microwave irradiation;	To a 5 ml vial, 6-CHLORO-2N- [L, 2, 4] triazolo [4, 3-alpha] quinolin-1-one (50 mg, 0.228 mmol), 3- aminophenylboronic acid (41.5 mg, 0.274 mmol), cesium carbonate (148. 6 mg, 0.456 MMOL), and tetrakis (trisphenylphosphine) palladium (18 mg, 7 MOL%) were added in 3 ml of dioxane: water (4: 1). The reaction was subject to microwave irradiation at 165C for 20min. After cooling down, the upper layer was separated and concentrated. The residue was dissolved in the minimum amount of DMSO, filtered through a 2GEL cartridge, and the filtrate purified by HPLCto yield th etitle compound as a white solid (75.5%). TH NMR (400MHz, DMSO-d6) : 4.60 (s, 2H), 5.28 (s, br, 1H), 7.10-7. 78 (m, 8H), 9.04 (d, J = 8.4Hz, 1H), 12.58 (s, 1H). m/z : 291

Reference： [1]Patent: WO2004/81008,2004,A1 .Location in patent: Page 139

13
[ 843661-15-4 ]
[ 87199-15-3 ]
4-[[3'-(hydroxymethyl)-4-biphenylyl](3,3,5,5-tetramethylcyclohexylidene)methyl]phenol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 160℃; for 0.416667h;	A sealed tube containing 4- [ (4-BROMOPHENYL) (3,3, 5,5- TETRAMETHYLCYCLOHEXYLIDENE) METHYL] PHENOL (1) (0. 20 G, 0.50 MMOL), 3- (hydroxymethyl) phenyl boronic acid (0.16 g, 1.0 MMOL), Pd (PPh3) 4 (58 mg, 0.05 MMOL), 2 M Na2CO3 (4 mL) and DME (4 mL) was heated at 160 C for 25 minutes. Cooled to room temperature, the mixture was extracted with EtOAc. The EtOAc extracts were combined and washed with water, brine, dried over NA2SO4, filtered, and the filtrate was concentrated to give the crude product as dark brown oil. The crude product was purified by chromatography on a silica gel column eluted with a gradient from hexanes to 30% EtOAc in hexanes to give 0.14 g (66%) of the title compound (247) as pale yellow solid. mp 197-198 C. H NMR (400 MHz, DMSO- d6) : 8 0.89 (s, 12H), 1.25 (s, 2H), 1.93 (s, 4H), 4.52 (d, J = 5.9 Hz, 2H), 5.20 (t, J = 5. 9HZ, 1H), 6.66 (d, J=8. 4HZ, 2H), 6.95 (d, J=8.4 Hz, 2H), 7.19 (d, J = 8. 0 HZ, 2H), 7.26 (d, J = 7. 5 HZ, 1 H), 7.37 (t, J=7.6 Hz, 1H), 7.48 (d, J=7.7 Hz, 1H), 7.52- 7.58 (m, 3H), 9.27 (s, 1 H). LCMS (ESI) : m/z 427 (M + H) +, 425 (M-H)-.

Reference： [1]Patent: WO2005/12220,2005,A2 .Location in patent: Page/Page column 172

14
3-benzoyl-(4-fluoro-8-trifluoromethyl)quinolin-4-yl trifluoromethanesulfonate [ No CAS ]
[ 87199-15-3 ]
[ 854766-07-7 ]

Yield	Reaction Conditions	Operation in experiment
96%	With potassium phosphate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; for 3h;Heating / reflux;	A solution of (3-benzoyl-8-(trifluoromethyl)quinolin-4-yl trifluoromethanesulfonate). (3.0 g, 6.0 mmol), 3-hydroxymethylphenylboronic acid (1.5 g, 10 mmol), K3PO4 (3.0 g) and Pd(PPh3)4 (0.30 g) in dioxane (30 ml) was heated to reflux. After 3 hr, the reaction was cooled and poured into water. The aqueous layer was extracted with EtOAc, dried, concentrated to give an oil which was purified by column chromatography (eluent 30% EtOAc/Hexane) to give the title compound as a foam (2.6 g, 96%); MS (ESI) m/z 407([M+H]+); 1H NMR (DMSO) delta 9.149 (s, 1H), 8.33 (d, 1H, J=7.1 Hz), 7.96 (d, 1H), 7.8 Hz), 7.80 (t, 1H, J=7.4 Hz), 7.62 (d, 2H, H=7.1 Hz), 7.55 (t, 1H, J=7.5 Hz), 7.40-7.28 (m, 5H), 7.18-7.14 (m, 1H), 5.23 (t, 1H, J=5.6 Hz), 4.41 (d, 1H, J=5.6 Hz).

Reference： [1]Patent: US2005/131014,2005,A1 .Location in patent: Page/Page column 38

15
[ 666730-32-1 ]
[ 87199-15-3 ]
{3-[3-(6,7-Dimethoxy-quinolin-4-yloxy)-6-methyl-pyridin-2-yl]-phenyl}-methanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
43%		Compound 231: {3-[3-(6,7-Dimethoxy-quinolin-4-yloxy)-6-methyl-pyridin-2-yl]-phenyl}-methanol; Toluene (1 ml) and a saturated aqueous sodium hydrogencarbonate solution (0.5 ml) were added to 4-(2-iodo-6-methyl-pyridin-3-yloxy)-6,7-dimethoxy-quinoline (compound 116) (50 mg), tetrakis-triphenylphosphine palladium (14 mg), and (3-hydroxymethyl)-phenylboronic acid (90 mg) under an argon atmosphere, and the mixture was stirred 80C overnight. The reaction solution was cooled to room temperature, a 1 N aqueous sodium hydroxide solution was then added thereto, and the mixture was extracted with chloroform. The chloroform layer was then washed with water and was dried over anhydrous sodium sulfate. The solvent was removed by distillation under the reduced pressure, and the residue was purified by thin layer chromatography using chloroform-methanol to give the title compound (20 mg, yield 43%). 1H-NMR (CDCl3, 400 MHz): delta 2.69 (s, 3H), 4.03 (s, 3H), 4.03 (s, 3H), 4.63 (s, 2H), 6.35 (d, J = 5.4 Hz, 1H), 7.17 - 7.34 (m, 4H), 7.43 (d, J = 8.3 Hz, 1H), 7.50 (s, 1H), 7.71 - 7.80 (m, 1H), 7.86 (s, 1H), 8.22 (d, J = 5.2 Hz, 1H) Mass spectrometric value (ESI-MS, m/z): 403 (M+1)+

Reference： [1]Patent: EP1548008,2005,A1 .Location in patent: Page/Page column 123

16
[ 844443-88-5 ]
[ 87199-15-3 ]
[ 844443-89-6 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; In ethanol; water; toluene; at 120℃; for 0.25h;microwave irradiation;	A mixture of 4-iodo-1-(4-methoxy-benzyl)-1H-pyrazole-3-carboxylic acid phenylamide (50 mg; 0.11 mmol), bis(tri-tert-butylphosphine)palladium (12 mg), potassium carbonate (100 mg; 0.66 mmol) and 3- (hydroxmethyl)benzene boronic acid (21 mg; 0.14mmo.) in ethanol/toluene/water (4 ml:1 ml:1 ml) was heated at 120 C (50 W) for 15 minutes in a CEM Discover microwave synthesiser. The reaction was evaporated and the residue partitioned between ethyl acetate and brine. The ethyl acetate layer was separated, dried (MgSO4), filtered and evaporated and the crude material purified by flash column chromatography eluting with 1 :2 then 2:1 ethyl acetate/hexane. Product containing fractions were combined and evaporated to give 60 mg of 4-(3- hydroxymethyl-phenyl)-1 -(4-methoxy-benzyl)-1H-pyrazole-3-carboxylic acid phenylamide.
	With potassium carbonate; In ethanol; water; toluene; at 120℃; for 0.25h;microwave irradiation;	A mixture of 4-iodo-1-(4-methoxy-benzyl)-1H-pyrazole-3-carboxylic acid phenylamide (50 mg; 0.11 mmol), bis(tri-tert-butylphosphine)palladium (12 mg), potassium carbonate (100 mg; 0.66 mmol) and 3- (hydroxmethyl)benzene boronic acid (21 mg; 0.14mmo.) in ethanol/toluene/water (4 ml:1 ml:1 ml) was heated at 120 C (50 W) for 15 minutes in a CEM Discover microwave synthesiser. The reaction was evaporated and the residue partitioned between ethyl acetate and brine. The ethyl acetate layer was separated, dried (MgSO4), filtered and evaporated and the crude material purified by flash column chromatography eluting with 1 :2 then 2:1 ethyl acetate/hexane. Product containing fractions were combined and evaporated to give 60 mg of 4-(3- hydroxymethyl-phenyl)-1 -(4-methoxy-benzyl)-1H-pyrazole-3-carboxylic acid phenylamide.
	With potassium carbonate;bis(tri-tert-butylphosphine)palladium; In ethanol; water; toluene; at 120℃; for 0.25h;	A mixture OF 4-IODO-1-(4-METHOXY-BENZYL)-LH-PYRAZOLE-3-CARBOXYLIC acid phenylamide (50 mg; 0.11 mmol), bis (tri-tert-butylphosphine) palladium (12 mg), potassium carbonate (100 mg; 0.66 mmol) and 3- (hydroxmethyl) benzene boronic acid (21MG ; 0. 14MMOL) in ethanol/toluene/water (4 ml: L ml: L ml) was heated at 120 C (50 W) for 15 minutes in a CEM Discover microwave synthesiser. The reaction was evaporated and the residue partitioned between ethyl acetate and brine. The ethyl acetate layer was separated, dried (MGS04), filtered and evaporated and the crude material purified by flash column chromatography eluting with 1: 2 then 2: 1 ethyl acetate/hexane. Product containing fractions were combined and evaporated to give 60 mg of 4- (3-HYDROXYMETHYL-PHENYL)-1- (4-METHOXY-BENZYL)-LH-PYRAZOLE-3- carboxylic acid phenylamide.

Reference： [1]Patent: WO2006/77425,2006,A1 .Location in patent: Page/Page column 205
[2]Patent: WO2006/77424,2006,A1 .Location in patent: Page/Page column 185
[3]Patent: WO2005/12256,2005,A1 .Location in patent: Page/Page column 208

17
[ 52127-83-0 ]
[ 87199-15-3 ]
[ 873566-62-2 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 105℃; for 4h;	A mixture of 3-hydroxymethylphenylboronic acid (4.5 g), 2,4-dichloro- 6-morpholinopyrimidine (7 g), tetrakis(triphenylphosphine)palladium(0) (0.35 g), a saturated aqueous solution of sodium carbonate (12.7 g) and 1,4-dioxane (250 ml) was stirred and heated to 1050C for 4 hours under an atmosphere of nitrogen. The resultant reaction mixture was evaporated. The residue was partitioned between ethyl acetate and water. The organic phase was washed with brine, dried over magnesiun sulphate and evaporated. The material so obtained was triturated under methanol. The resultant solid was isolated, washed with <n="76"/>methanol and dried. There was thus obtained 4-chloro-2-(3-hydroxymethylphenyl)~ 6-morpholinopyrimidine (2.25 g); NMR Spectrum: (DMSOd6) 3.58-3.81 (m, 8H)5 4.57 (d, 2H)5 5.27 (t, IH)5 6.9 (s, lH)57.41-7.47 (m, 2H)5 8.15-8.19 (m, IH)5 8.27 (s, IH); Mass Spectrum: M+H4" 306.
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 105℃; for 4h;	A mixture of 3-hydroxymethylphenylboronic acid (4.5 g), 2,4-dichloro- 6-morpholinopyrimidine (7 g), tetrakis(triphenylphosphine)palladium(0) (0.35 g), a saturated aqueous solution of sodium carbonate (12.7 g) and 1,4-dioxane (250 ml) was stirred and heated to 1050C for 4 hours under an atmosphere of nitrogen. The resultant reaction mixture <n="79"/>was evaporated. The residue was partitioned between ethyl acetate and water. The organic phase was washed with brine, dried over magnesiun sulphate and evaporated. The material so obtained was triturated under methanol. The resultant solid was isolated, washed with methanol and dried. There was thus obtained 4-chloro-2~(3-hydroxymethylphenyl)- 6-morpholinorhoyrimidine (2.25 g); NMR Spectrum: (DMSOd6) 3.58-3.81 (m, 8H), 4.57 (d, 2H), 5.27 (t, IH), 6.9 (s, lH),7.41-7.47 (m, 2H), 8.15-8.19 (m, IH)5 8.27 (s, IH); Mass Spectrum: M+H+ 306.
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 105℃; for 4h;	A mixture of 3-hydroxymethylphenylboronic acid (4.5 g), 2,4-dichloro- 0 6-morpholinopyrimidine (7 g), tetrakis(triphenylphosphine)palladium(0) (0.35 g)5 a saturated aqueous solution of sodium carbonate (12.7 g) and 1,4-dioxane (250 ml) was stirred and heated to 105C for 4 hours under an atmosphere of nitrogen. The resultant reaction mixture <n="78"/>was evaporated. The residue was partitioned between ethyl acetate and water. The organic phase was washed with brine, dried over magnesiun sulphate and evaporated. The material so obtained was triturated under methanol. The resultant solid was isolated, washed with methanol and dried. There was thus obtained 4-chloro-2-(3-hydroxymethylphenyl)- 6-morpholinopyrimidine (2.25 g); NMR Spectrum: (DMSOd6) 3.58-3.81 (m, 8H), 4.57 (d, 2H), 5.27 (t, IH), 6.9 (s, lH),7.41-7.47 (m, 2H), 8.15-8.19 (m, IH), 8.27 (s, IH); Mass Spectrum: M+H+ 306.

With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 105℃; for 4h;

A mixture of 3-hydroxymethylphenylboronic acid (4.5 g), 2,4-dichloro-6-morpholinopyrimidine (7 g), tetrakis(triphenylphosphine)palladium(0) (0.35 g), a saturatedaqueous solution of sodium carbonate (12.7 g) and 1,4-dioxane (250 ml) was stirred and heatedto 105C for 4 hours under an atmosphere of nitrogen. The resultant reaction mixture wasevaporated. The residue was partitioned between ethyl acetate and water. The organic phasewas washed with brine, dried over magnesiun sulphate and evaporated. The material soobtained was triturated under methanol. The resultant solid was isolated, washed withmethanol and dried. There was thus obtained 4-chloro-2-(3-hydroxymethylphenyl)-6-morpholinopyrimidine (2.25 g); NMR Spectrum: (DMSOde) 3.58-3.81 (m, 8H), 4.57 (d,2H), 5.27 (t, 1H), 6.9 (s, lH),7.41-7.47 (m, 2H), 8.15-8.19 (m, 1H), 8.27 (s, 1H); MassSpectrum: M+H* 306.

Reference： [1]Patent: WO2007/66099,2007,A1 .Location in patent: Page/Page column 74-75
[2]Patent: WO2007/66102,2007,A1 .Location in patent: Page/Page column 76-77
[3]Patent: WO2007/66103,2007,A1 .Location in patent: Page/Page column 76-77
[4]Patent: WO2006/5918,2006,A1 .Location in patent: Page/Page column 84

18
[ 876617-65-1 ]
[ 87199-15-3 ]
(4'-{5-methyl-4-[2-(2R-methyl-pyrrolidin-1-yl)-ethyl]-oxazol-2-yl}-biphenyl-3-yl)-methanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
61%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 90℃; for 1h;Microwave;	Add 2-(4-bromo-phenyl)-5-methyl-4- [2-(2/?-methyl-pyrrolidin-1 -yl)-ethyl] -oxazole (0.200 g, 0.573 mmol), Pd(Ph3P)4 (0.025 g, 0.029 mmol), 3-hydroxymethyl boronic acid (0.131 g, 0.859 mmol), 2N Na2C03 (1.4 mL), and 1,4-dioxane (2 mL) to a microwave vessel. Microwave at 30 W, 90 C for 60 minutes. Add dichloromethane and water. Wash the organic layer with saturated sodium chloride solution. Dry the organic layer over Na2SC>4, filter, and concentrate. Purify on silica gel eluting with 10% ammoniated methanol in dichloromethane to give (4'-{5-methyl-4-[2-(2/?-methyl-pyrrolidin-l-yl)-ethyl]-oxazol-2-yl}-biphenyl-3-yl)-methanol (0.131 g, 61%): MS (m/e): 377 (M+l).Treat the recovered material (0.131 g, 0.348 mmol) with IN HC1 (383 uL, 0.383 mmol) in ether, concentrate, and lyophilize to give the title compound (143 mg): MS (m/e): 377 (M+l).

Reference： [1]Patent: WO2006/19833,2006,A1 .Location in patent: Page/Page column 99-100

19
[ 3430-23-7 ]
[ 87199-15-3 ]
[ 351458-12-3 ]

Yield	Reaction Conditions	Operation in experiment
79%		(a) Intermediate 69a-[3-(5-Bromo-4-methyl-pyridin-3-yl)-phenyl]-methanol: The title compound was prepared in 79% yield from <strong>[3430-23-7]3,5-dibromo-4-methyl-pyridine</strong> and 3-(hydroxymethyl)-phenyl-boronic acid similar to the procedure for intermediate 53a. 1H NMR (300 MHz, CDCl3) delta 8.62 (s, 1H), 8.22 (s, 1H), 7.42-7.46 (m, 2H), 7.29 (s, 1H), 7.16-7.20 (m, 1H), 4.76 (d, 2H, J=5.7 Hz), 2.48 (t, 1H, J=5.7 Hz), 2.32 (s, 3H). Anal. (C13H12BrNO.0.2 H2O) C, H, N.

Reference： [1]Patent: US2002/161022,2002,A1

20
[ 937046-98-5 ]
[ 87199-15-3 ]
[ 937048-34-5 ]

Yield	Reaction Conditions	Operation in experiment
45%	With sodium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; water; toluene; at 75℃;	Intermediate B (3.00 g, 14.1 mmol) and 3-hydroxymethylphenyl boronic acid (2.57 g, 16.9 mmol) were suspended in 36 ml_ of 8:1 to toluene:dioxane and degassed via a vacuum/N2 purge (3 cycles). 1, 1'-Bis(diphenylphosphino)ferrocenepalladium(ll) chloride- complex with CH2CI2 (0.52 g, 0.7 mmol ) was added followed by 21 mL of 2M aqueous sodium carbonate and the mixture was heated with stirring to 75 0C overnight. The mixture was allowed to cool to room temp (solid mass formed) and diluted with water and EtOAc. The mixture was filtered through Celite and the pad washed well with EtOAc followed by MeOH. The filtrate was poured into a separatory funnel and the layers were separated. The organic phase was washed with brine, dried (Na2SO^, filtered and concentrated in vacuo. The residue was purified by Isco (Red-Sep 120, eluting with 75% - 100% EtOAc.hexa?es) to provide 1.54 g (45%) of the title compound as an off white solid. 1H-NMR (DMSO-dfe) .5 7.98 (s, 1H), 7.91 (m, 2H), 7.22 (bs, 2H), 7.38 (t, 1 H), 7.24 (d, 1 H), 6.99 (s, 2H), 5.25 (t, 12H), 4.55 (d, 2H); LC-MS [M+H]+ = 241.3, RT = 1.51 min.

Reference： [1]Patent: WO2007/56170,2007,A2 .Location in patent: Page/Page column 194

21
[ 22726-00-7 ]
[ 87199-15-3 ]
[ 875455-52-0 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate;bis-triphenylphosphine-palladium(II) chloride; In methanol; toluene; at 80℃; for 18h;	A mixture of <strong>[22726-00-7]3-bromobenzamide</strong> (3 g, 15.1 mmol), [3-(hydroxymethyl)- phenyl]boronic acid (3 g, 19.6 mmol), PdCl2(PPh3)2 (0.46 g, 0.66 mmol), and potassium carbonate (3.6 g, 26.2 mmol) in Toluene/MeOH (10:1, 40 mL) was stirred at 80 C for 18 h. The resulting black mixture was cooled to room temperature, filtered through celite, and poured into a EtO Ac/brine mixture. The two layers were separated and the aqueous was extracted with EtOAc (3x). The organics were combined, dried over sodium sulfate, filtered, and evaporated to dryness. The residue was purified by flash chromatography on silica gel eluting with a mixture of EtOAc/Hexane to give 3'-(hydroxymethyl)biphenyl-3-carboxamide as a solid

Reference： [1]Patent: WO2006/14918,2006,A2 .Location in patent: Page/Page column 74

22
[ 825643-73-0 ]
[ 87199-15-3 ]
2-(3,5-bis-trifluoromethyl-phenyl)-N-[4-(4-fluoro-2-methyl-phenyl)-6-(3-hydroxymethyl-phenyl)-pyridin-3-yl]-N-methyl-isobutyramide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With sodium carbonate; triphenylphosphine;palladium diacetate; In 1,2-dimethoxyethane; at 90℃; for 12h;	A mixture of 126 mg (0.236 mmol) 2-(3,5-bis-trifluoromethyl-phenyl)-N-[6-chloro-4-(4-fluoro-2-methyl-phenyl)-pyridin-3-yl]-N-methyl-isobutyramide, 40 mg (0.26 mmol) 3-(hydroxymethyl)phenylboronic acid, 0.5 ml of a 2 M aqueous sodium carbonate solution and 2 ml 1,2-dimethoxyethane was degassed by three freeze-thaw cycles. After addition of 3 mg (0.01 mmol) palladium acetate and 6 mg (0.02 mmol) triphenylphosphine the reaction mixture was stirred under argon at 90 C. for 12 h. After cooling to room temperature the reaction mixture was diluted with 2 M sodium carbonate solution and extracted with three portions of tert-butyl methyl ether. The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo. Flash chromatography gave 117 mg (82%) of the title compound as a white solid. MS m/e (%): 605 (M+H+, 100).

Reference： [1]Patent: US2006/30600,2006,A1 .Location in patent: Page/Page column 15

23
[ 622860-38-2 ]
[ 55552-70-0 ]
[ 1765-93-1 ]
[ 10365-98-7 ]
[ 32316-92-0 ]
[ 5122-94-1 ]
[ 98546-51-1 ]
[ 78887-39-5 ]
[ 128796-39-4 ]
[ 1692-25-7 ]
[ 135145-90-3 ]
[ 94839-07-3 ]
[ 1423-26-3 ]
[ 150255-96-2 ]
[ 126747-14-6 ]
[ 179113-90-7 ]
[ 139301-27-2 ]
[ 87199-15-3 ]
[ 89641-18-9 ]
[ 308103-40-4 ]
[ 149104-88-1 ]
[ 622860-55-3 ]
9-hydroxy-4-(4-methylsulfanylphenyl)-6H-pyrrolo[3,4-c]carbazole-1,3-dione [ No CAS ]
[ 622860-48-4 ]
4-(4-fluorophenyl)-9-hydroxy-6H-pyrrolo[3,4-c]carbazole-1,3-dione [ No CAS ]
4-(9-hydroxy-1,3-dioxo-1,2,3,6-tetrahydro-pyrrolo[3,4-c]carbazol-4-yl)-benzonitrile [ No CAS ]
3-(9-Hydroxy-1,3-dioxo-1,2,3,6-tetrahydro-pyrrolo[3,4-c]carbazol-4-yl)-benzonitrile [ No CAS ]
4-(2,5-dichlorophenyl)-9-hydroxy-6H-pyrrolo[3,4-c]carbazole-1,3-dione [ No CAS ]
9-Hydroxy-4-(3-hydroxymethyl-phenyl)-6H-pyrrolo[3,4-c]carbazole-1,3-dione [ No CAS ]
4-(2-Acetyl-phenyl)-9-hydroxy-6H-pyrrolo[3,4-c]carbazole-1,3-dione [ No CAS ]
9-hydroxy-4-(4-methanesulfonylphenyl)-6H-pyrrolo[3,4-c]carbazole-1,3-dione [ No CAS ]
9-hydroxy-4-(4-trifluoromethylphenyl)-6H-pyrrolo[3,4-c]carbazole-1,3-dione [ No CAS ]
9-hydroxy-4-(3-trifluoromethylphenyl)-6H-pyrrolo[3,4-c]carbazole-1,3-dione [ No CAS ]
4-Furan-2-yl-9-hydroxy-6H-pyrrolo[3,4-c]carbazole-1,3-dione [ No CAS ]
9-Hydroxy-4-(3-trifluoromethoxy-phenyl)-6H-pyrrolo[3,4-c]carbazole-1,3-dione [ No CAS ]
9-Hydroxy-4-(4-trifluoromethoxy-phenyl)-6H-pyrrolo[3,4-c]carbazole-1,3-dione [ No CAS ]
9-hydroxy-4-naphthalen-2-yl-6H-pyrrolo[3,4-c]carbazole-1,3-dione [ No CAS ]
4-(1,3-benzodioxol-5-yl)-9-hydroxy-6H-pyrrolo[3,4-c]carbazole-1,3-dione [ No CAS ]
4-(2,4-dimethoxy-pyrimidin-5-yl)-9-hydroxy-6H-pyrrolo[3,4-c]carbazole-1,3-dione [ No CAS ]
4-biphenyl-4-yl-9-hydroxy-6H-pyrrolo[3,4-c]carbazole-1,3-dione [ No CAS ]
N-[3-(9-hydroxy-1,3-dioxo-1,2,3,6-tetrahydro-pyrrolo[3,4-c]carbazol-4-yl)-phenyl]acetamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; water; at 90℃; for 4h;Combinatorial reaction / High throughput screening (HTS);Product distribution / selectivity;	EXAMPLE 36The Preparation of a series of compounds using multiple parallel synthetic techquires from 9-hydroxy-4-iodopyrrolo[3,4-c]carbazole-1,3(2H,6H)-dione prepared as in Example 7 Combichem Procedure 1; In a 8 ml screw cap vial was added a solution of 9-Hydroxy-4-iodo-6H-pyrrolo[3,4-c]carbazole-1,3-dione, (0.1 mmol) prepared as in example 7 in dioxane (1 ml), a solution of Reagent 1 (see table) (0.1 mmol) in 1:1 dioxane/2.5 M K2CO3 (1 ml) and [1,1'Bis(diphenylphosphino)ferrocene]-dichloropalladium(II) complex with dichloromethane (0.003 g, 0.0037 mmol). The vial was capped and the reaction mixture was shaken for 4 hours at 90 C. After cooling to room temperature, the solution was was removed under vacuum. Purification was carried out via reverse-phase HPLC (3% n-propanol in acetonitrile and 3% n-propanol in water as the eluent; C-18 column). The products were characterised by mass spectral analysis (See Table 1).

Reference： [1]Patent: US7094798,2006,B1 .Location in patent: Page/Page column 40-42

24
[ 905590-33-2 ]
aqueous potassium carbonate [ No CAS ]
[ 247940-06-3 ]
[ 87199-15-3 ]
4-(3,4-diethoxyphenyl)-N-{4-[3-(hydroxymethyl)phenyl]-6-phenylpyridin-2-yl}-4-oxobutanamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	tris-(dibenzylideneacetone)dipalladium(0);	Example 136 4-(3,4-diethoxyphenyl)-N-{4-[3-(hydroxymethyl)phenyl]-6-phenylpyridin-2-yl}-4-oxobutanamide 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-hydroxymethylphenyl)boronic acid (19.0 mg) as starting materials and in the same manner as in Example 119, 4-(3,4-diethoxyphenyl)-N-{4-[3-(hydroxymethyl)phenyl]-6-phenylpyridin-2-yl}-4-oxobutanamide (15.6 mg) was obtained. HPLC (220 nm) purity 98% (retention time 1.91 min) MS (ESI+, m/e) 525 (M+H)

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

25
[ 905590-58-1 ]
aqueous potassium carbonate [ No CAS ]
[ 247940-06-3 ]
[ 87199-15-3 ]
4-(2,3-dihydro-1-benzofuran-5-yl)-N-{4-[3-(hydroxymethyl)phenyl]-6-phenylpyridin-2-yl}-4-oxobutanamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	tris-(dibenzylideneacetone)dipalladium(0);	Example 167 4-(2,3-dihydro-1-benzofuran-5-yl)-N-{4-[3-(hydroxymethyl)phenyl]-6-phenylpyridin-2-yl}-4-oxobutanamide 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-hydroxymethylphenyl)boronic acid (19.0 mg) as starting materials and in the same manner as in Example 119, 4-(2,3-dihydro-1-benzofuran-5-yl)-N-{4-[3-(hydroxymethyl)phenyl]-6-phenylpyridin-2-yl}-4-oxobutanamide (6.8 mg) was obtained. HPLC (220 nm) purity 99% (retention time 1.84 min) MS (ESI+, m/e) 479 (M+H)

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

26
[ 6952-59-6 ]
[ 87199-15-3 ]
[ 226070-51-5 ]

Yield	Reaction Conditions	Operation in experiment
93%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; for 10h;Heating / reflux;	Reference Example 133 3'-(hydroxymethyl)biphenyl-3-carbonitrile To a solution of 3-bromobenzonitrile (1.20 g, 6.58 mmol) in toluene (40 mL) was added a solution of tetrakistriphenylphosphinepalladium (0.38 g, 0.33 mmol), 2N aqueous sodium carbonate solution (21 mL) and <strong>[87199-15-3][3-(hydroxymethyl)phenyl]boronic acid</strong> (1.00 g, 6.58 mmol) in EtOH (19 mL), and the mixture was heated under reflux for 10 hr under nitrogen atmosphere. The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=1/9?1/1) to give the title compound as a yellow oil (1.28 g, 93%). 1H-NMR (300MHz, CDCl3) delta: 4.79 (2H, d, J = 5.3 Hz), 7.39-7.67 (6H, m), 7.82 (1H, d, J = 7.6 Hz), 7.87 (1H, s), 1H hidden.

Reference： [1]Patent: EP1953148,2008,A1 .Location in patent: Page/Page column 172

27
[ 1062205-50-8 ]
[ 87199-15-3 ]
[ 1062205-39-3 ]

Yield	Reaction Conditions	Operation in experiment
70%	With sodium hydrogencarbonate;tetrakis(triphenylphosphine) palladium(0); In water; N,N-dimethyl-formamide; at 175℃; for 0.25h;	{3-[6-morpholin-4-yl-9-(2-piperidin-1-ylethyl)-9H-purin-2-yl]phenyl}methanol was prepared from 2-Chloro-6-morpholin-4-yl-9-(2-piperidin-1-yl-ethyl)-9H-purine (130 mg, 0.37 mmol, 1 eq), saturated aqueous NaHCO3 solution (0.37 ml), (Ph3P)4Pd (24 mg, 0.02 mmol, 0.05 eq), and 3-hydroxymethyl phenyl boronic acid (85 mg, 0.556 mmol, 1.5 eq) in DMF (1.5 mL) by heating in a microwave apparatus to 175 C. for 15 min. The solvent is removed and the material dissolved in DMSO (2 mL) and purified by HPLC to give the product (109 mg, 70% yield; MS (ESI) m/z 423.4).

Reference： [1]Patent: US2008/233127,2008,A1 .Location in patent: Page/Page column 36

28
[ 1174766-04-1 ]
[ 87199-15-3 ]
[ 1174765-62-8 ]

Yield	Reaction Conditions	Operation in experiment
57%	With sodium hydrogencarbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 130℃; for 0.5h;Microwave irradiation;	Step 3To a microwave processing tube dimethoxyethane (8 mL), saturated aqueous NaHCO3 (3 mL), (Ph3P)4Pd (113 mg, 0.098 mmol), 3-(hydroxymethyl)phenyl-boronic acid (445 mg, 2.93 mmol) and tert-butyl 4-(2-chloro-6-(3,6-dihydro-2H-pyran-4-yl)-9H-purin-9-yl)piperidine-1-carboxylate (820 mg, 1.96 mmol) were added and the vessel was sealed. The mixture was heated to 130 C. for 30 minutes. The solvents were removed on a rotary evaporator and the crude compound was purified by silica gel chromatography (10% MeOH in CHCl3) to give the product as a white solid (280 mg, 57% yield) of white solid.

Reference： [1]Patent: US2009/192176,2009,A1 .Location in patent: Page/Page column 44

29
C₉H₈ClN₅O [ No CAS ]
[ 87199-15-3 ]
[ 1174765-70-8 ]

Yield	Reaction Conditions	Operation in experiment
42%	With sodium hydrogencarbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 175℃; for 0.25h;Microwave irradiation;	Step 3In a microwave vial was suspended 2-cloro-6-morpholin-4-yl-8-aza-purine (110 mg, 0.46 mmol), 3-hydroxymethylphenylboronic acid (140 mg, 0.92 mmol, 2 eq), (Ph3P)4Pd (27 mg, 0.2 mmol, 0.05 eq), and saturated aqueous NaHCO3 (0.5 mL) in DME (3 mL). The reaction mixture was heated under stirring to 175 C. for 15 minutes. After the reaction was completed, the solvent was removed in vacuo and the crude product was purified by semi-prep-HPLC using ACN/water/TFA as mobile phase. After removal of solvents, the product (60 mg, 42% yield) was obtained as off-white solid, MS (ESI) m/z 309.1.

Reference： [1]Patent: US2009/192176,2009,A1 .Location in patent: Page/Page column 46

30
[ 1186401-83-1 ]
[ 76-05-1 ]
[ 87199-15-3 ]
(3-{7-[2-(dimethylamino)ethyl]-4-morpholin-4-yl-7H-pyrrolo[2,3-h]quinazolin-2-yl}phenyl)methanol trifluoroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%		A mixture of 2-chloro-7-(2-(dimethylamino)ethyl)-4-morpholin-4-yl-7H-pyrrolo[2,3h]quinazoline (62 mg, 0.17 mmol), 3-(hydroxymethyl)phenylboronic acid (39 mg, 0.26 mmol), Pd(PPh3)4 (10 mg, 5 mol %), dimethoxyethane (DME, 3 mL) and 2M Na2CO3 (0.5 mL) was heated at 130 C. for 0.5 h in microwave oven. The reaction mixture was cooled to room temperature, and filtered through a pad of Celite, washed with THF. The filtrate was concentrated under reduced pressure, and the residue was subjected to HPLC separation to give the title compound as yellow solid (TFA salt, 72 mg, 78% yield). MS (ESI) m/z 432.4.

Reference： [1]Patent: US2009/227575,2009,A1 .Location in patent: Page/Page column 24-25

31
[ 1189852-09-2 ]
[ 87199-15-3 ]
[ 1189852-41-2 ]

Yield	Reaction Conditions	Operation in experiment
62%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; N,N-dimethyl-formamide; at 100℃;	A suspension of 4-ter£-butyl-JV-(7-chloro-2-methylpyrazolo[ 1 ,5-alpha]pyrimidin-5- yl)benzamide (IK, 40 mg, 1.0 equivalent), 3-(hydroxymethyl)phenylboronic acid (1.9 equivalents), Pd(PPtLs)4 (0.10 equivalent), and Na2CO3 (4.0 equivalents) in N2-saturated 5:1 DMF/H2O (0.05 M with respect to IK) was stirred at 100 0C overnight. After cooling, the mixture was diluted with brine and extracted with EtOAc. Combined organic layers were dried over MgSO4, filtered and concentrated. The crude product was purified by chromatography (SiO2, gradient of 40 to 50% EtOAc/hexanes). The product was then recrystallized from CH2Cl2-hexanes to give the titled compound (62%) as a white solid. 1H NMR (400MHz, CDCl3) delta ppm 1.37 (s, 9H) 2.50 (s, 3H) 4.83 (d, J=6.1 Hz, 2H) 6.29 (s, IH) 7.44-7.71 (m, 5H) 7.88 (d, J=8.3 Hz, 2H) 8.03 (s, IH) 8.15 (s, IH) 8.59 (s, IH).

Reference： [1]Patent: WO2009/123986,2009,A1 .Location in patent: Page/Page column 168

32
[ 1189852-09-2 ]
[ 87199-15-3 ]
4-(2-hydroxypropan-2-yl)-N-(7-p-tolylpyrazolo[1,5-a]pyrimidin-5-yl)benzamide trifluoroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
35%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; N,N-dimethyl-formamide; at 100℃;	A suspension of 4-ter£-butyl-JV-(7-chloro-2-methylpyrazolo[ 1 ,5-alpha]pyrimidin-5- yl)benzamide (IK, 40 mg, 1.0 equivalent), 3-(hydroxymethyl)phenylboronic acid (1.9 equivalents), Pd(PPtLs)4 (0.10 equivalent), and Na2CO3 (4.0 equivalents) in N2-saturated 5:1 DMF/H2O (0.05 M with respect to IK) was stirred at 100 0C overnight. After cooling, the mixture was diluted with brine and extracted with EtOAc. Combined organic layers were dried over MgSO4, filtered and concentrated. The crude product was purified by chromatography (SiO2, gradient of 40 to 50% EtOAc/hexanes). The product was then recrystallized from CH2Cl2-hexanes to give the titled compound (62%) as a white solid. 1H NMR (400MHz, CDCl3) delta ppm 1.37 (s, 9H) 2.50 (s, 3H) 4.83 (d, J=6.1 Hz, 2H) 6.29 (s, IH) 7.44-7.71 (m, 5H) 7.88 (d, J=8.3 Hz, 2H) 8.03 (s, IH) 8.15 (s, IH) 8.59 (s, IH).

Reference： [1]Patent: WO2009/123986,2009,A1 .Location in patent: Page/Page column 179

33
[ 1189852-17-2 ]
[ 87199-15-3 ]
[ 1190045-80-7 ]

Yield	Reaction Conditions	Operation in experiment
44%	With sodium hydrogencarbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; water; at 110℃; for 0.333333h;Microwave irradiation;	In a 2 niL microwave vial were placed lambda/-(7-chloro-2-cyclopropylpyrazolo[l ,5- alpha]pyrimidin-5-yl)-4-(2-hydroxypropan-2-yl)benzamide (2 J, 100 mg, 0.27 mmol), 3- (hydroxymethyl)phenylboronic acid (51 mg, 0.34 mmol) and[l,r-bis(diphenylphosphino)ferrocene]-dichloropalladium(II) (9.9 mg, 14 mumol). To the sealed vial was then added 1,4-dioxane (1 ml) and saturated aqueous NaHCO3 (0.5 ml) to give a suspension. The mixture was then heated in the microwave at 110 0C for 20 minutes. After cooling to room temperature, the reaction mixture was partitioned between brine and EtOAc. The aqueous layer was extracted once more with EtOAc, and the combined organic layers were dried over MgSO4, filtered and concentrated in vacuo. The crude product was purified by recrystallization from ether and EtOAC to give the titled compound (52 mg, 44 % yield) as an off-white solid. 1H NMR (400 MHz, DMSO-d6) delta = 11.18 (s, 1 H), 8.02 (d, J = 8.6 Hz, 2 H), 8.00 - 7.96 (m, 2 H), 7.95 (s, 1 H), 7.61 (d, J = 8.6 Hz, 2 H), 7.59 - 7.54 (m, 2 H), 6.28 (s, 1 H), 5.44 - 5.37 (m, 1 H), 5.19 (s, 1 H), 4.63 (d, J= 5.6 Hz, 2 H), 2.12 - 2.03 (m, 1 H), 1.04 - 0.98 (m, 2 H), 0.88 - 0.81 (m, 2 H); ESI-MS: m/z 443.3 (M+H)+.

Reference： [1]Patent: WO2009/123986,2009,A1 .Location in patent: Page/Page column 287

34
[ 591-18-4 ]
[ 87199-15-3 ]
[ 1000063-64-8 ]

Yield	Reaction Conditions	Operation in experiment
80%	With sodium carbonate;dichlorobis(triphenylphosphine)palladium[II]; In 1,2-dimethoxyethane;	Step 1: (3'-bromobiphenyl-3-yl)methanol 94 To a 0.2 M solution of <strong>[87199-15-3][3-(hydroxymethyl)phenyl]boronic acid</strong> in DME were sequentially added 1-bromo-3-iodobenzene (0.83 eq.) and a 2M solution of Na2CO3 (3.0 eq.). The reaction mixture was degassed, trans-bis(triphenylphosphine)palladium(II) chloride (0.01 eq.) was added and it was stirred at 80 C. for 6 h. After cooling down to RT the reaction mixture was diluted with EtOAc and washed with saturated aq. NaHCO3, 1N HCl and brine. The residue was dried (Na2SO4) and evaporated under reduced pressure to afford an oil which was purified by flash chromatography (SiO2, PE:EtOAc=8:2) to afford the title compound 94 as an oil (80%). 1H NMR (400 MHz, DMSO-d6, 300 K) delta 7.87 (s, 1H), 7.71 (d, J 7.7, 1H), 7.66 (bs, 1H), 7.59 (t, J 6.8, 2H), 7.47 (t, J 7.7, 2H), 7.39 (d, J 7.7, 1H), 4.61 (s, 2H).
73%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 70℃; for 10h;Inert atmosphere;	In a nitrogen atmosphere, 12.0 g of 1-bromo-3-iodobenzene, 6.8 g of 3-(hydroxymethyl)phenylboronic acid, 27.0 g of sodium carbonate, 360 mL of toluene in a 1 L three-necked flask,120 mL of ethanol, 120 mL of water, and 3.7 g of tetrakistriphenylphosphine palladium were sequentially added,The mixture was stirred at 70 C. under reflux for 10 hours. After cooling to room temperature,The reaction solution was diluted with chloroform and washed with water three times.The organic layer was dried over magnesium sulfate.The crude product obtained by removing the solvent was purified by silica gel chromatography to obtain 8.2 g of T11 intermediate 3.(Yield 73%) was obtained.

Reference： [1]Patent: US2009/312241,2009,A1
[2]Patent: JP2020/70288,2020,A .Location in patent: Paragraph 0096; 0100-0102

35
[ 1202885-72-0 ]
[ 87199-15-3 ]
[ 1202884-44-3 ]

Yield	Reaction Conditions	Operation in experiment
50%	With sodium hydrogencarbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 120℃; for 1h;Microwave irradiation;	Step 4: Synthesis of [3-(4-morpholin-4-yl-7H-pyrrolo[2,3-d]pyrimidin-2-yl)phenyl]methanol To a 10 mL vial were added 2-chloro-4-morpholin-4-yl-7H-pyrrolo[2,3-d]pyrimidine (150 mg, 0.63 mmol), 3-hydroxymethylphenylboronic acid (144 mg, 0.94 mmol), Pd(PPh3)4 (36 mg, 5 mol %), 1,2-dimethoxyethane (DME, 2.5 mL) and saturated sodium bicarbonate aqueous solution (1.5 mL). The resulting mixture was heated at 120 C. for 1 h in microwave oven. The reaction mixture was cooled to room temperature. The aqueous phase was extracted with EtOAc, and the combined organic solution was concentrated under reduced pressure. The residue was subjected to HPLC separation to give the title compound as off-white solid (98 mg, 50% yield). MS(ESI) m/z 311.3. HRMS: calcd for C17H18N4O2+H+, 311.15025; found (ESI-FTMS, [M+H]1+), 311.15016.

Reference： [1]Patent: US2010/3250,2010,A1 .Location in patent: Page/Page column 20
[2]Journal of Medicinal Chemistry,2010,vol. 53,p. 3169 - 3182

36
[ 1031393-25-5 ]
[ 87199-15-3 ]
[ 1198164-16-7 ]

Yield	Reaction Conditions	Operation in experiment
80%	With pyridine;copper diacetate; In dichloromethane; at 20℃; for 12h;Molecular sieve;	Preparation Example 3; Preparation of 1-(3-(bromomethyl)phenoxy)-4-(1,1,1,3,3,3-hexafluoro-2-(methoxymethoxy(propan-2-yl)-2-propylbenzene; a) Preparation of (3-(4-(1,1,1,3,3,3-hexafluoro-2-(methoxymethoxy)propan-2-yl)-2-propylphenoxy)phenyl) methanol; A solution of 4-(1,1,1,3,3,3-hexafluoro-2-(methoxymethoxy)propan-2-yl)-2-propylphenol (1.58 g, 4.56 mmol) in dichloromethane (45 mL) was added with molecular sieves 4 A (3.00 g), 3-(hydroxymethyl)phenylbronic acid (2.08 g), copper acetate(II) (1.66 g) at room temperature, and then with pyridine (1.85 mL). The resultant mixture was stirred for 12 hours. The reaction solution was filtered using celite and the filtrate was concentrated in vacuum. The residue was purified using silica-gel column chromatography (hexane/ethyl acetate) and the title compound (1.65 g, yield 80%) was obtained as a colorless crystalline powder.1H-NMR (CDCl3) delta: 0.95 (3H, t, J=7.6 Hz), 1.62-1.71 (2H, m), 2.68 (2H, t, J=7.6 Hz), 3.56 (3H, s), 4.70-4.71 (2H, m), 4.86 (2H, s), 6.83 (1H, d, J=8.9 Hz), 6.90-6.92 (1H, m), 7.03-7.15 (2H, m), 7.31-7.47 (3H, m).

Reference： [1]Patent: US2010/48610,2010,A1 .Location in patent: Page/Page column 16

37
[ 767-69-1 ]
[ 87199-15-3 ]
[ 1200437-70-2 ]

Reference： [1]Journal of Medicinal Chemistry,2010,vol. 53,p. 316 - 324

38
[ 2004-03-7 ]
[ 87199-15-3 ]
[ 1200437-71-3 ]

Reference： [1]Journal of Medicinal Chemistry,2010,vol. 53,p. 316 - 324

39
[ 28033-01-4 ]
[ 87199-15-3 ]
[ 1235468-00-4 ]

Yield	Reaction Conditions	Operation in experiment
86%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In methanol; toluene; for 48h;Inert atmosphere; Reflux;	A flask containing a mixture of 3-(hydroxymethyl)phenylboronic acid (0.88 g, 5.79 mmol), methyl 3-amino-2,6-dibromoisonicotinate (1.5 g, 4.8 mmol), tetrakistriphenylphosphine Pd(O) (0.335 g, 0.290 mmol), sodium carbonate (1.23 g, 11.6 mmol) was flushed with nitrogen and toluene (12 mL), and MeOH (4 niL) were added. The reaction was heated at reflux under nitrogen for 48 hr. It was partitioned between EtOAc and water and the organic phase was separated, washed with brine, dried with sodium sulfate, and the solvent removed. Chromatography (step gradient elution with DCM containing 0 to 15% EtOAc) afforded methyl 3-amino-6-bromo-2- (3-(hydroxymethyl)phenyl)isonicotinate (1.4 g, 4.2 mmol, 86 % yield) as a yellow solid. MS (ESI) m/z 339.02 (M+H). 1H NMR (400 MHz, chloroform-d) delta ppm 7.80 (1 H, s), 7.58 (1 H, s), 7.40 - 7.55 (3 H, m), 5.94 (2 H, br. s.), 4.74 (2 H, d, J=5.79 Hz), 3.92 (3 H, s), 1.77 (1 H, t, J=5.92 Hz).

Reference： [1]Patent: WO2010/80474,2010,A1 .Location in patent: Page/Page column 209

40
[ 108-86-1 ]
[ 87199-15-3 ]
[ 69605-90-9 ]

Yield	Reaction Conditions	Operation in experiment
89%	With C44H32Cl4I2N4P2Pd2; tetrabutylammomium bromide; caesium carbonate; In water; at 100℃; for 12h;Inert atmosphere;	General procedure: A Schlenk tube was charged with the prescribed amount of catalyst, aryl halide (1.0 mmol), 3-(hydroxymethyl)phenylboronicacid (1.5 mmol), TBAB (1.0 mmol), the selected base (3.0 mmol), and water under nitrogen atmosphere. The reaction mixture was heated at 100 C for 12 h. After cooling,the mixture was extracted with CH2Cl2, the solvent was evaporated,and the product was separated by passing through a silica gel column with CH2Cl2/ethyl acetate (5:1) aseluent. The products 2f, 2j, 2l, and 2o were new compounds and were determined by 1H and C13 NMR. Other products were characterized by comparison with data in the literature.

Reference： [1]Beilstein Journal of Organic Chemistry,2011,vol. 7,p. 310 - 319
[2]Bulletin of the Korean Chemical Society,2015,vol. 36,p. 2355 - 2358
[3]Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry,2010,vol. 49,p. 565 - 572

41
[ 104-92-7 ]
[ 87199-15-3 ]
[ 20854-56-2 ]

Yield	Reaction Conditions	Operation in experiment
85%	With C44H32Cl4I2N4P2Pd2; tetrabutylammomium bromide; caesium carbonate; In water; at 100℃; for 12h;Inert atmosphere;	General procedure: A Schlenk tube was charged with the prescribed amount of catalyst, aryl halide (1.0 mmol), 3-(hydroxymethyl)phenylboronicacid (1.5 mmol), TBAB (1.0 mmol), the selected base (3.0 mmol), and water under nitrogen atmosphere. The reaction mixture was heated at 100 C for 12 h. After cooling,the mixture was extracted with CH2Cl2, the solvent was evaporated,and the product was separated by passing through a silica gel column with CH2Cl2/ethyl acetate (5:1) aseluent. The products 2f, 2j, 2l, and 2o were new compounds and were determined by 1H and C13 NMR. Other products were characterized by comparison with data in the literature.

42
[ 591-50-4 ]
[ 87199-15-3 ]
[ 69605-90-9 ]

Reference： [1]Applied Organometallic Chemistry,2012,vol. 26,p. 430 - 437
[2]Beilstein Journal of Organic Chemistry,2011,vol. 7,p. 310 - 319
[3]Tetrahedron Letters,2012,vol. 53,p. 6100 - 6103,4
[4]Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry,2010,vol. 49,p. 565 - 572

43
[ 586-78-7 ]
[ 87199-15-3 ]
[ 62038-00-0 ]

Yield	Reaction Conditions	Operation in experiment
94%	With C44H32Cl4I2N4P2Pd2; tetrabutylammomium bromide; caesium carbonate; In water; at 100℃; for 12h;Inert atmosphere;	General procedure: A Schlenk tube was charged with the prescribed amount of catalyst, aryl halide (1.0 mmol), 3-(hydroxymethyl)phenylboronicacid (1.5 mmol), TBAB (1.0 mmol), the selected base (3.0 mmol), and water under nitrogen atmosphere. The reaction mixture was heated at 100 C for 12 h. After cooling,the mixture was extracted with CH2Cl2, the solvent was evaporated,and the product was separated by passing through a silica gel column with CH2Cl2/ethyl acetate (5:1) aseluent. The products 2f, 2j, 2l, and 2o were new compounds and were determined by 1H and C13 NMR. Other products were characterized by comparison with data in the literature.

Reference： [1]European Journal of Organic Chemistry,2015,vol. 2015,p. 3558 - 3567
[2]Beilstein Journal of Organic Chemistry,2011,vol. 7,p. 310 - 319
[3]Bulletin of the Korean Chemical Society,2015,vol. 36,p. 2355 - 2358
[4]Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry,2010,vol. 49,p. 565 - 572

44
[ 183438-24-6 ]
[ 87199-15-3 ]
[ 1092568-90-5 ]

Yield	Reaction Conditions	Operation in experiment
41%	With potassium phosphate tribasic trihydrate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 90℃; for 14h;Inert atmosphere;	a) Preparation of [3-(5-bromopyrimidin-2-yl)phenyl]methanol9.107 g of K3PO4*3H2O (42.9 mmol) are dissolved in 120 ml of dioxane and 14 ml of water in a 250 ml flask, 6.111 g of 5-bromo-2-iodopyrimidine (21.5 mmol) and 3.91 g of 3-(hydroxymethyl)benzeneboronic acid (25.74 mmol) are added, and the reaction vessel is flushed with N2 for 15 min with stirring. 0.75 g of tetrakis(triphenylphosphine)palladium(0) (0.65 mmol) are then added, and the mixture is stirred under an N2 atmosphere at an oil-bath temperature of 90 C. for 14 h.For work-up, the reaction mixture is diluted with MTBE, water is added, the mixture is filtered through Celite with suction, the aqueous phase is separated off from the organic phase, extracted a further 2× with MTBE, and the combined organic phase is dried over Na2SO4 and evaporated to dry-ness.The purification is carried out by chromatography.Yield: 2.49 g of [3-(5-bromopyrimidin-2-yl)phenyl]methanol (8.83 mmol)=41% as pale-yellow solid.
	With potassium phosphate tribasic trihydrate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 90℃; for 18h;Inert atmosphere;	EXAMPLE 11The preparation of 3-{3-[5-(2-dimethylaminoethoxy)pyrimidin-2-yl]benzyl}-5-methyl-3H-oxazolo[4,5-b]pyridin-2-one (?A109?) is carried out analogously to the following scheme:Step aPreparation of [3-(5-bromopyrimidin-2-yl)phenyl]methanol750 mg (0.65 mmol) of tetrakis(triphenylphosphine)palladium are added to a solution, kept under nitrogen, of 6.11 g (21.5 mmol) of 5-bromo-2-iodopyrimidine, 3.91 g (25.7 mmol) of 3-(hydroxymethyl)benzeneboronic acid and 9.11 g (42.9 mmol) of tripotassium phosphate trihydrate in 120 ml of dioxane and 14 ml of water, and the mixture is stirred at 90 C. for 18 hours. The reaction mixture is cooled to room temperature, tert-butyl methyl ether and water are added, and the mixture is filtered through kieselguhr. The organic phase of the filtrate is separated off, dried over sodium sulfate and evaporated. The residue is chromatographed on a silica-gel column with dichloromethane/methanol as eluent.Product: 2.49 g; m.p. 114-117 C.; ESI: 265, 267 (M+H); HPLC: Rt=2.51 min (method B).
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 80℃; for 18h;Inert atmosphere; Reflux;	1.2 A solution of 318 g (3.00 mmol) of sodium carbonate in 1.5 l of water is added to a solution, kept under nitrogen, of 427 g (1.50 mol) of 5-bromo-2-iodopyrimidine in 1.5 l of toluene. This mixture is warmed to 80 C., and 34.7 g (30 mmol) of tetrakis(triphenylphosphine)palladium and a solution of 228 g (1.50 mol) of 3-(hydroxymethyl)benzeneboronic acid in 3 l of ethanol are added. The reaction mixture is subsequently heated at reflux for 18 hours. The reaction mixture is cooled to room temperature, filtered and partitioned between water and tent-butyl methyl ether. The organic phase is dried over sodium sulfate and concentrated to a volume of 1 l. The precipitate formed is filtered off with suction and washed with toluene: [3-(5-bromopyrimidin-2-yl)-phenyl]methanol as colourless crystals; ESI 265, 267.

	With sodium carbonate;bis(triphenylphosphine)palladium(II)-chloride; In ethanol; water; ethyl acetate; toluene;	Preparation of [3-(5-bromopyrimidin-2-yl)phenyl]methanol A solution of 70.0 g (660 mmol) of sodium carbonate in 325 ml of water is added to a solution, kept under nitrogen, of 95.0 g (332 mmol) of 5-bromo-2-iodopyrimidine in 325 ml of toluene, and the mixture is heated to 80 C. 2.3 g (3.3 mmol) of bis(triphenylphosphine)palladium(II) chloride are added, and a solution of 50.0 g (329 mmol) of 3-(hydroxymethyl)benzeneboronic acid in 650 ml of ethanol is subsequently added dropwise. The reaction mixture is stirred at 80 C. for 18 hours. The reaction mixture is cooled to room temperature and filtered. 1 l of ethyl acetate and 1 l of water are added to the filtrate. The organic phase is separated off, dried over sodium sulfate and evaporated. The residue is recrystallised from 2-propanol: [3-(5-bromopyrimidin-2-yl)-phenyl]methanol as pale-yellow crystals; m.p. 115-116 C.; LCMS 265, 267.
	With potassium phosphate tribasic trihydrate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 90℃; for 18h;Inert atmosphere;	Step a:750 mg (0.65 mmol) of tetrakis(triphenylphosphine)palladium are added to a solution, kept under nitrogen, of 6.11 g (21.5 mmol) of 5-bromo-2-iodopyrimidine, 3.91 g (25.7 mmol) of 3-(hydroxymethyl)benzeneboronic acid and 9.11 g (42.9 mmol) of tripotassium phosphate trihydrate in 120 ml of dioxane and 14 ml of water, and the mixture is stirred at 90 C. for 18 hours. The reaction mixture is cooled to room temperature, tert-butyl methyl ether and water are added, and the mixture is filtered through kieselguhr. The organic phase of the filtrate is separated off, dried over sodium sulfate and evaporated. The residue is chromatographed on a silica-gel column with dichloromethane/methanol as eluent:product: 2.49 g; m.p. 114-117, ESI: 265, 267 (M+H), HPLC: Rt.=2.51 min (method B).
	With sodium carbonate;bis-triphenylphosphine-palladium(II) chloride; In ethanol; water; toluene; at 80℃; for 18h;Inert atmosphere;	2.1 A solution of 70.0 g (660 mmol) of sodium carbonate in 325 ml of water is added to a solution, kept under nitrogen, of 95.0 g (332 mmol) of 5-bromo-2-iodopyrimidine in 325 ml of toluene, and the mixture is heated to 80 C. 2.3 g (3.3 mmol) of bis(triphenylphosphine)palladium(II) chloride are added, and a solution of 50.0 g (329 mmol) of 3-(hydroxymethyl)benzeneboronic acid in 650 ml of ethanol is subsequently added dropwise. The reaction mixture is stirred at 80 C. for 18 hours. The reaction mixture is cooled to room temperature and filtered. 1 l of ethyl acetate and 1 l of water are added to the filtrate. The organic phase is separated off, dried over sodium sulfate and evaporated. The residue is recrystallised from 2-propanol: [3-(5-bromopyrimidin-2-yl)phenyl]methanol as pale-yellow crystals; ESI 265,267.
	With potassium phosphate tribasic trihydrate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 90℃; for 18h;Inert atmosphere;	Step a Preparation of [3-(5-bromopyrimidin-2-yl)phenyl]methanol 750 mg (0.65 mmol) of tetrakis(triphenylphosphine)palladium are added to a solution, kept under nitrogen, of 6.11 g (21.5 mmol) of 5-bromo-2-iodo-pyrimidine, 3.91 g (25.7 mmol) of 3-(hydroxymethyl)benzeneboronic acid and 9.11 g (42.9 mmol) of tripotassium phosphate trihydrate in 120 ml of dioxane and 14 ml of water, and the mixture is stirred at 90 C. for 18 hours. The reaction mixture is cooled to room temperature, tert-butyl methyl ether and water are added, and the mixture is filtered through kieselguhr. The organic phase of the filtrate is separated off, dried over sodium sulfate and evaporated. The residue is chromatographed on a silica-gel column with dichloromethane/methanol as eluent; product: 2.49 g; m.p. 114-117; ESI: 265, 267 (M+H); HPLC: Rt.=2.51 min (method A).

Reference： [1]Patent: US2010/311733,2010,A1 .Location in patent: Page/Page column 20
[2]Patent: US2010/280030,2010,A1 .Location in patent: Page/Page column 50
[3]Patent: US2010/273796,2010,A1 .Location in patent: Page/Page column 19-20
[4]Patent: US2011/135600,2011,A1
[5]Patent: US2011/257181,2011,A1 .Location in patent: Page/Page column 21
[6]Patent: US2011/269765,2011,A1 .Location in patent: Page/Page column 22
[7]Patent: US2011/269756,2011,A1 .Location in patent: Page/Page column 22

45
[ 851916-84-2 ]
[ 87199-15-3 ]
[ 1187820-68-3 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; toluene; at 80℃; for 16h;Inert atmosphere;	2.3 [3-(2-Chloroimidazo[1,2-a]pyridin-6-yl)phenyl]methanol In a round-bottomed flask, 760 mg of <strong>[851916-84-2]6-bromo-2-chloroimidazo[1,2-a]pyridine</strong> are placed in 25 ml of toluene and 8 ml of ethanol and the mixture is degassed with argon for 10 min. After the addition of 230 mg of tetrakis(triphenylphosphine)palladium, the mixture is stirred for 5 min at ambient temperature and then 650 mg of 3-(hydroxymethyl)-phenylboronic acid and 8 ml of a 2M solution of sodium carbonate are added. The reaction mixture is heated at 80 C. for 16 h and then cooled to ambient temperature and concentrated under reduced pressure. The residue is taken up between water and ethyl acetate and the organic phase is separated, dried over magnesium sulphate and concentrated under reduced pressure. The oil obtained is purified by silica gel chromatography, elution being carried out with a heptane/ethyl acetate mixture. 550 mg of compound are obtained. 1H NMR spectrum (DMSO-d6, delta in ppm): 4.6 (d, 2H); 5.3 (t, 1H); from 7.35 to 7.75 (m, 6H); 8.1 (s, 1H); 8.85 (s, 1H). M+H=259.

Reference： [1]Patent: US2011/65727,2011,A1 .Location in patent: Page/Page column 12

46
[ 1300583-87-2 ]
[ 87199-15-3 ]
[ 1300584-02-4 ]

Yield	Reaction Conditions	Operation in experiment
44%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; N,N-dimethyl-formamide; at 80℃; for 12.5h;Inert atmosphere;	Example 61 2-((4-amino-3-(3-(hydroxymethyl)phenyl)-1H-pyrazolo[3,4-d]pyrimidin-1-yl)methyl)-3-phenyl-4H-chromen-4-one To a solution of Example 57a (0.250 g, 0.50 mmoles) in DMF (5 ml), ethanol (2.5 ml) and water (2.5 ml), 3-hydroxymethylphenylboronic acid (0.115 g, 0.757 mmoles) and sodium carbonate (0.267 g, 2.53 mmoles) were added and the system is degassed for 30 min. Tetrakis triphenylphosphine Palladium (0.115 g, 0.099 mmoles) was added under nitrogen atmosphere and heated to 80 C. After 12 h, the reaction mixture was celite filtered, concentrated and extracted with ethyl acetate. The organic layer was dried over sodium sulphate and concentrated under reduced pressure. The crude product was purified by column chromatography with methanol:dichloromethane to afford the title compound as brown solid (0.116 g, 44% yield). MP: 219-223 C. 1H-NMR (delta ppm, DMSO-d6, 400 MHz): delta 8.23 (s, 1H), 8.05 (dd, J=8.0, 1.6 Hz, 1H), 7.77 (m, 1H), 7.58 (s, 1H), 7.50 (m, 3H), 7.44 (d, J=8.5 Hz, 1H), 7.41-7.31 (m, 6H), 5.52 (s, 2H), 5.27 (t, J=5.8 Hz, 1H), 4.57 (d, J=5.7 Hz, 2H). Mass: 476.31 (M++1).

Reference： [1]Patent: US2011/118257,2011,A1 .Location in patent: Page/Page column 112

47
trifluoromethanesulfonic acid diphenyl(trifluoromethyl)sulfonium salt [ No CAS ]
[ 87199-15-3 ]
[ 349-75-7 ]

Reference： [1]Chemical Communications,2011,vol. 47,p. 9516 - 9518

48
[ 57699-28-2 ]
[ 15164-44-0 ]
[ 87199-15-3 ]
[ 1360002-20-5 ]

Reference： [1]Organic and Biomolecular Chemistry,2012,vol. 10,p. 1670 - 1679

49
[ 98141-42-5 ]
[ 87199-15-3 ]
[ 1292902-35-2 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In acetonitrile; at 85℃; for 20h;Inetrt atmosphere;	EXAMPLE 2 Preparation of [3-(1-methyl-6-morpholin-4-yl-1H-pyrazolo[3,4-d]pyrimidin-4-yl)phenyl]methanol ("A33?) 2.1 A solution of 100 mg of "2?, 107.4 mg of 3-(hydroxymethyl)-benzeneboronic acid, 56.85 mg of sodium carbonate and 28.17 mg of tetrakis(triphenylphosphine)palladium(0) in 4 ml of acetonitrile is stirred at 85 for 20 h under argon. The mixture is subjected to conventional work-up and purified by means of preparative HPLC, giving 62 mg of [3-(6-chloro-1-methyl-1H-pyrazolo[3,4-d]pyrimidin-4-yl)phenyl]methanol ("5?).

Reference： [1]Patent: US2012/208808,2012,A1 .Location in patent: Page/Page column 22

50
[ 76-09-5 ]
[ 87199-15-3 ]
[ 443776-76-9 ]

Reference： [1]Organic Letters,2013,vol. 15,p. 4850 - 4853

51
[ 87199-15-3 ]
[ 364794-80-9 ]

Reference： [1]Organic Letters,2013,vol. 15,p. 4850 - 4853

52
[ 87199-15-3 ]
[ 883738-27-0 ]

Reference： [1]Organic Letters,2013,vol. 15,p. 4850 - 4853

53
[ 4595-60-2 ]
[ 87199-15-3 ]
[ 892502-12-4 ]

Yield	Reaction Conditions	Operation in experiment
88%	With C44H32Cl4I2N4P2Pd2; tetrabutylammomium bromide; caesium carbonate; In water; at 100℃; for 12h;Inert atmosphere;	General procedure: A Schlenk tube was charged with the prescribed amount of catalyst, aryl halide (1.0 mmol), 3-(hydroxymethyl)phenylboronicacid (1.5 mmol), TBAB (1.0 mmol), the selected base (3.0 mmol), and water under nitrogen atmosphere. The reaction mixture was heated at 100 C for 12 h. After cooling,the mixture was extracted with CH2Cl2, the solvent was evaporated,and the product was separated by passing through a silica gel column with CH2Cl2/ethyl acetate (5:1) aseluent. The products 2f, 2j, 2l, and 2o were new compounds and were determined by 1H and C13 NMR. Other products were characterized by comparison with data in the literature.
37%	With palladium diacetate; sodium carbonate; triphenylphosphine; In propan-1-ol; water; at 95℃; for 2.5h;Inert atmosphere;	In a 4mL vial, palladium(II) acetate (0.9 mg, 4.01 muiotaetaomicron), triphenylphosphine (2.7 mg, 10.29 mumol), 2M aqueous solution of sodium carbonate (0.55 ml, 1.100 mmol) and water (0.3 ml, 16.65 mmol) were successively added to a mixture of 2- <strong>[4595-60-2]bromopyrimidine</strong> (120 mg, 0.755 mmol) and (3-(hydroxymethyl)phenyl)boronic acid (121 mg, 0.796 mmol) in 1-propanol (1.5 ml, 19.97 mmol) under nitrogen. The mixture was stirred at 95 C for 2.5 hours. The mixture was quenched with water and the product was extracted three times with AcOEt. The combined organic layers were washed once with sat. NaHCO3, once with brine, dried over anh. Na2SC"4 and concentrated. The residue was purified on ISCO using a REDISEP Gold 12 g column (Hex/EtOAc) to give the title material (52 mg, 37%) as a clear oil. LC (Method B): 1.372 min. MS(ESI) calcd for C11H12N20 [M+H]+ m/z 187.0866, found 187.0898. 1H NMR (400 MHz, acetone) ppm 8.87 (d, J=5.1 Hz, 2 H) 8.47 - 8.55 (m, 1 H) 8.37 (dt, J=7.4, 1.6 Hz, 1 H) 7.42 - 7.56 (m, 2 H) 7.38 (t, J=4.7 Hz, 1 H) 4.68 - 4.79 (m, 2 H) 4.31 (t, J=5.9 Hz, 1 H).

Reference： [1]Bulletin of the Korean Chemical Society,2015,vol. 36,p. 2355 - 2358
[2]Patent: WO2013/163241,2013,A1 .Location in patent: Paragraph 00132

54
[ 62129-39-9 ]
[ 87199-15-3 ]
C₂₁H₂₅NO₅ [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2014,vol. 79,p. 8652 - 8658

55
[ 878207-92-2 ]
[ 87199-15-3 ]
methyl 6-[3-(hydroxymethyl)phenyl]-3-methyl-pyridine-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
51.4%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate; In 1,4-dioxane; water; at 110℃; for 2h;Inert atmosphere;	To a solution of methyl 6-chloro-3-methyl-pyridine-2- carboxylate (1.0 g, 5.39 mmol) in 1,4-dioxane (17.9 ml) and H20 (2.9 ml) is added (3- (hydroxymethyl)phenyl)boronic acid (0.982 g, 6.47 mmol) followed by K2C03 (1.86 g, 13.47 mmol) and PdCl2(dppf)*CH2Cl2 (131.9 mg, 0.13 mmol). The reaction mixture is purged with argon for 5 minutes and then heated at 110C. After 2 hours, the reaction is cooled to room temperature, diluted with water and extracted with EtOAc. The combined organic layers are dried over magnesium sulfate, filtered, and concentrated. The residue is purified by silica gel flash chromatography using 70% EtOAc in hexane to afford methyl 6-[3-(hydroxymethyl)phenyl]-3-metliyl-pyridine-2-carboxylate (0.713 g, 51.4%). Mass spectrum (m/z): 258.0 (M+l)+.

Reference： [1]Patent: WO2015/94912,2015,A1 .Location in patent: Page/Page column 39-40

56
[ 16932-45-9 ]
[ 87199-15-3 ]
(2',6'-dimethoxybiphenyl-3-yl)methanol [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2015,vol. 2015,p. 3558 - 3567

57
[ 16932-45-9 ]
[ 87199-15-3 ]
2,6-dimethoxy-2'-hydroxymethylbiphenyl [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2015,vol. 2015,p. 3558 - 3567

58
[ 56423-63-3 ]
[ 87199-15-3 ]
[ 1313237-38-5 ]

Yield	Reaction Conditions	Operation in experiment
85%	With C44H32Cl4I2N4P2Pd2; tetrabutylammomium bromide; caesium carbonate; In water; at 100℃; for 12h;Inert atmosphere;	General procedure: A Schlenk tube was charged with the prescribed amount of catalyst, aryl halide (1.0 mmol), 3-(hydroxymethyl)phenylboronicacid (1.5 mmol), TBAB (1.0 mmol), the selected base (3.0 mmol), and water under nitrogen atmosphere. The reaction mixture was heated at 100 C for 12 h. After cooling,the mixture was extracted with CH2Cl2, the solvent was evaporated,and the product was separated by passing through a silica gel column with CH2Cl2/ethyl acetate (5:1) aseluent. The products 2f, 2j, 2l, and 2o were new compounds and were determined by 1H and C13 NMR. Other products were characterized by comparison with data in the literature.

Reference： [1]Bulletin of the Korean Chemical Society,2015,vol. 36,p. 2355 - 2358

59
[ 1201924-32-4 ]
[ 87199-15-3 ]
alkyl 3-amino-2,4-dimethylbenzoate [ No CAS ]
3-[[6-[3-(hydroxymethyl)phenyl]-3-methyl-pyridine-2-carbonyl]amino]-2,4-dimethyl-benzoic acid [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2016,vol. 26,p. 931 - 935

60
[ 1201924-32-4 ]
[ 87199-15-3 ]
alkyl 4-amino-3,5-dimethylbenzoate [ No CAS ]
4-[[6-[3-(hydroxymethyl)phenyl]-3-methyl-pyridine-2-carbonyl]amino]-3,5-dimethyl-benzoic acid [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2016,vol. 26,p. 931 - 935

61
[ 87199-15-3 ]
[ 195044-14-5 ]
(3-(6-(tert-butyl)pyridin-2-yl)phenyl)methanol [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2017,vol. 56,p. 1614 - 1618
Angew. Chem.,2017,vol. 129,p. 1636 - 1640,5

62
[ 87941-55-7 ]
[ 87199-15-3 ]
(3-(1-trityl-1H-imidazol-4-yl)phenyl)methanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate; In 1,4-dioxane; water; at 150℃; for 0.5h;Inert atmosphere; Microwave irradiation;	A mixture of (3-(hydroxymethyl)phenyl)boronic acid (58.6 mg, 0.3 85 mmol),4-bromo-1-trityl-1H-immdazole (100 mg, 0.257 mmol), PdC12(dppf)-DCM adduct (10 mg,0.013 mmol) and potassium carbonate (178 mg, 1.28 mmol) in 1,4-dioxane (2 mL) and water (0.5 mL) was sparged 3 times with Ar. The reaction mixture then was heated at 150C in a microwave for 30 mm. The mixture was partitioned between DCM and water. The organic layer was washed with brine. The combined aqueous layers were extracted withDCM. The combined organics were dried with Na2SO4, filtered, and concentrated. The crude was purified by flash chromatography to give 278A (89 mg, 83%) as a white solid.MS(ESI) m/z 417.2 (M+H).

Reference： [1]Patent: WO2017/40449,2017,A1 .Location in patent: Paragraph 00623

63
[ 4027-57-0 ]
[ 87199-15-3 ]
C₁₄H₁₆N₂O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
35.54%	With pyridine; copper diacetate; In dichloromethane; at 25℃; under 775.743 Torr; for 16h;Molecular sieve;	[1157] to <strong>[4027-57-0]ethyl 3-methyl-1H-pyrazole-5-carboxylate</strong> (3 g, 19.46 mmol), [3-(hydroxymethyl)phenyl]boronic acid (4.44 g, 29.19 mmol), 4a ms (8 g) and pyridine (1.69 g, 21.41 mmol, 1.8 ml) in DCM (70 ml) was added Cu(OAc)2 (4.59 g, 25.30 mmol), the mixture was stirred at 25 C for 16h under 02 balloon (15 psi). The reaction mixture was filtered to get rid of 4a ms and catalyst, and then the filtrate was concentrated. The residue was purified by preparatory-hplc (tfa condition). Compound 229a (1.8 g, yield: 35.54%) was obtained as a colorless oil. 1H NMR (400mhz, CDCl3) delta 7.48 - 7.35 (m, 3h), 7.32 - 7.28 (m, 1h), 6.81 (s, 1h), 4.71 (s, 2h), 4.22 (q, j = 7.0 hz, 2h), 2.35 (s, 3h), 1.24 (t, j = 7.0 hz, 3h).

Reference： [1]Patent: WO2018/64119,2018,A1 .Location in patent: Paragraph 1157

64
[ 258515-65-0 ]
[ 87199-15-3 ]
tert-butyl 7-(3-(hydroxymethyl)phenyl)-3,4-dihydroisoquinoline-2(1H)-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81.8%	With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In 1,2-dimethoxyethane; for 10h;Reflux; Inert atmosphere;	General procedure: Toa solution of compound 5a (5.0 g,16.0 mmol) in DME (60 mL) was added 3-(hydroxymethyl)phenyl)boronic acid (2.9g, 19.0 mmol), Pd(PPh3)4 (0.4 g, 0.3 mmol) and 2M cesiumcarbonate solution (12 mL), and then heated to reflux under argon atmosphere.After 10 h, the reaction mixture was washed with brine, dried over Na2SO4and concentrated under reduced pressure. The residue was purified by silica gelcolumn chromatography (PET/EA = 5:1, v/v)to afford compound 7a as yellow oil(4.7 g, 85.4%).

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2018,vol. 28,p. 3050 - 3056

65
[ 201940-08-1 ]
[ 87199-15-3 ]
tert-butyl 5-(3-(hydroxymethyl)phenyl)isoindoline-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78.1%	With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In 1,2-dimethoxyethane; for 10h;Reflux; Inert atmosphere;	General procedure: Toa solution of compound 5a (5.0 g,16.0 mmol) in DME (60 mL) was added 3-(hydroxymethyl)phenyl)boronic acid (2.9g, 19.0 mmol), Pd(PPh3)4 (0.4 g, 0.3 mmol) and 2M cesiumcarbonate solution (12 mL), and then heated to reflux under argon atmosphere.After 10 h, the reaction mixture was washed with brine, dried over Na2SO4and concentrated under reduced pressure. The residue was purified by silica gelcolumn chromatography (PET/EA = 5:1, v/v)to afford compound 7a as yellow oil(4.7 g, 85.4%).

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2018,vol. 28,p. 3050 - 3056

66
[ 87199-15-3 ]
5-nitro-3-thiocyanato-1H-indole [ No CAS ]
[ 874-97-5 ]

Reference： [1]Journal of Sulfur Chemistry,2018,vol. 39,p. 507 - 515

67
[ 2987-46-4 ]
[ 87199-15-3 ]
[ 874-97-5 ]

Reference： [1]Journal of Sulfur Chemistry,2018,vol. 39,p. 507 - 515

68
[ 62802-42-0 ]
[ 87199-15-3 ]
(3-(5-fluoropyrimidin-2-yl)phenyl)methanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In ethanol; water; toluene; at 80 - 90℃;Inert atmosphere;	Under nitrogen, a solution of sodium carbonate (4.24g, 40 mmol) in water (20 mL) was added to asolution of <strong>[62802-42-0]2-chloro-5-fluoropyrimidine</strong> 4 (2.47 mL, 20 mmol) in toluene (60 mL), and the mixture washeated to 80 C. Bis(triphenylphosphine)palladium(II) chloride (701.9 mg, 1 mmol) was added, and asolution of 3-(hydroxymethyl)phenylboronic acid (3.34 g, 22 mmol) in ethanol (20 mL) wassubsequently added dropwise. The reaction mixture was stirred at 90 C for 12 hours. The reactionmixture was cooled to room temperature and filtered. The aqueous phase was extracted with AcOEt(100 mL x 3). The combined organic layer was washed with H2O (30 mL) and brine (20 mL), and thendried over anhydrous Na2SO4, filtered and evaporated in vacuo. The residue was purified by flashchromatography over silica gel (petroleum/EtOAc = 10:13:1) to give(3-(5-fluoropyrimidin-2-yl)phenyl)methanol 5 (68%).
61%	With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In ethanol; water; toluene; at 80℃; for 18h;Inert atmosphere;	Adding sodium carbonate (66 mmol) in water (32 mL) to <strong>[62802-42-0]5-fluoro-2-chloropyrimidine</strong>(33 mmol) in a toluene solution (32 mL),Add bis(triphenylphosphine)palladium dichloride (0.33 mmol),A solution of hydroxymethylphenylboronic acid (32 mmol) in ethanol (65 mL) was added dropwise.Under nitrogen protection,Stir at 80 C for 18 hours,Cool to room temperature,filter,Ethyl acetate and water were added to the filtrate.Divide the organic phase,Dry over anhydrous sodium sulfate,The crude product was purified by silica gel column chromatography (ethyl acetate: petroleum ether, 8:1)Separated to a pale yellow solid,That is, intermediate 3a. Yield 61%.

Reference： [1]Molecules,2019,vol. 24
[2]Patent: CN108752322,2018,A .Location in patent: Paragraph 0111; 0114

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P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

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

[ CAS No. 87199-15-3 ]

Quality Control of [ 87199-15-3 ]

Related Doc. of [ 87199-15-3 ]

Product Details of [ 87199-15-3 ]

Calculated chemistry of [ 87199-15-3 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 87199-15-3 ]

Application In Synthesis of [ 87199-15-3 ]

[ 87199-15-3 ] Synthesis Path-Upstream 1~8

[ 87199-15-3 ] Synthesis Path-Downstream 1~68

Related Functional Groups of [ 87199-15-3 ]

Organoboron

Aryls

Alcohols

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 87199-15-3 ]