(4-(tert-Butoxycarbonyl)phenyl)boronic acid | Organoboron

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Quality Control of (4-(tert-Butoxycarbonyl)phenyl)boronic acid Purity: 98% SDS Specification

COA

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NMR

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CNMR

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HPLC

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Product Details of (4-(tert-Butoxycarbonyl)phenyl)boronic acid

CAS No. :	850568-54-6
Formula :	C₁₁H₁₅BO₄
M.W :	222.05
SMILES Code :	O=C(C1=CC=C(B(O)O)C=C1)OC(C)(C)C
MDL No. :	MFCD03411946
InChI Key :	QMVMDYSTJSUDKC-UHFFFAOYSA-N
Pubchem ID :	2773301

Safety of (4-(tert-Butoxycarbonyl)phenyl)boronic acid

GHS Pictogram:
Signal Word:	Warning
Hazard Statements:	H315-H319-H335
Precautionary Statements:	P261-P305+P351+P338

Application In Synthesis of (4-(tert-Butoxycarbonyl)phenyl)boronic acid

* 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.

Downstream synthetic route of [ 850568-54-6 ]

[ 850568-54-6 ] Synthesis Path-Downstream 1~35

1
[ 850568-54-6 ]
[ 636-98-6 ]
[ 914659-71-5 ]

References: [1]Journal of Organic Chemistry,2006,vol. 71,p. 7952 - 7966.

2
[ 14047-29-1 ]
[ 115-11-7 ]
[ 850568-54-6 ]

References: [1]Journal of Organic Chemistry,2006,vol. 71,p. 7952 - 7966.

3
[ 850568-54-6 ]
[ 956320-22-2 ]
(R)-3',5'-dichloro-4'-(1-morpholin-4-yl-2-oxo-pyrrolidin-3-ylmethyl)-biphenyl-4-carboxylic acid tert-butyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 60 - 80℃; for 3h;	Preparation 19B; (R)-3',5'-Dichloro-4'-(l-morpholin-4-yl-2-oxo-pyrrolidin-3-ylmethyl)-biphenyl-4- carboxylic acid tert-butyl ester; Bring a mixture of (R)-trifluoro-methanesulfonic acid 3,5-dichloro-4-(l- morpholin-4-yl-2-oxo-pyrrolidin-3-ylmethyl)-phenyl ester (0.19 g, 0.4 mmol), 4-t- butyloxycarbonylphenylboronic acid (0.106 g, 0.48 mmol), sodium carbonate (0.127 g, 1.2 mmol) in THF (10 mL) and water (3 mL) to 600C. To the mixture at 600C, add Pd(PPh3)4 (0.023 g, 0.02 mmol) and then raise reaction temperature to 800C and stir for 3 hours. Cool the reaction, dilute with ethyl acetate, and wash with water and brine. Dry the organic layer (Na2SO4), remove the solvent in vacuo to afford crude product, and then purify on silica gel column with 40percent ethyl acetate in hexanes to afford 0.15 g (74percent) of the titled product. MS (m/z): 461 (M+).

References: [1]Patent: WO2007/127688,2007,A2 .Location in patent: Page/Page column 50.

4
[ 850568-54-6 ]
[ 914659-79-3 ]

References: [1]Journal of Organic Chemistry,2006,vol. 71,p. 7952 - 7966.

5
[ 850568-54-6 ]
4'-hydroxyamino-biphenyl-4-carboxylic acid tert-butyl ester [ No CAS ]

References: [1]Journal of Organic Chemistry,2006,vol. 71,p. 7952 - 7966.

6
[ 850568-54-6 ]
4'-{4'-[(9H-fluoren-9-ylmethoxycarbonylamino)-methyl]-biphenyl-4-ylazo}-biphenyl-4-carboxylic acid tert-butyl ester [ No CAS ]

References: [1]Journal of Organic Chemistry,2006,vol. 71,p. 7952 - 7966.

7
[ 850568-54-6 ]
4'-{4'-[(9H-fluoren-9-ylmethoxycarbonylamino)-methyl]-biphenyl-4-ylazo}-biphenyl-4-carboxylic acid tert-butyl ester [ No CAS ]

References: [1]Journal of Organic Chemistry,2006,vol. 71,p. 7952 - 7966.

8
[ 850568-54-6 ]
[ 890842-84-9 ]
[ 890842-85-0 ]

Yield	Reaction Conditions	Operation in experiment
53%	With potassium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; water; at 80℃; for 1.5h;	d) tert-butyl 5-(6-r(tert-butoxycarbonyl)amino1pyridin-3-yl}-3-r4-(tert- butoxycarbonvQphenyl'j-1 /-/-pyrrolo[2,3-fc>lpyridine-1-carboxylateA solution of tert-butyl 3-bromo-5-{6-[(tert-butoxycarbonyl)amino]pyridin-3-yl}-1 H- pyrrolo[2,3-fo]pyridine-1-carboxylate (197 mg, 0.4 mmol), 4-t-butoxycarbonylphenyl boronic acid (111 mg, 0.5 mmol), K2CO3 (165 mg, 1.2 mmol) and bis(diphenylphosphino)ferrocene]dichloropalladium(ll) (50 mg) in dioxane (20 mL) and H2O (4 mL) was heated at 800C for 90 minutes. The reaction mixture was diluted with H2O and extracted with Et2O. The extracts were washed with H2O, dried and the solvent evaporated. The residue was purified by ISCO chromatography (12g silica column, 10percent EtOAc/hexane for 5 minutes grading to 20percent EtOAc/hexane over 1 minute, then 20percent EtOAc/hexane for 15 minutes) and afforded the titled compound as a white, crystalline solid, 124 mg (53percent). 1H NMR (400 MHz, CDCI3) .6 8.88 (d, 1H), 8.58 (d, 1 H), 8.40 (s, 1 H), 8.28 (d, 1H), 8.16 (m, 3H), 7.92(m, 1H), 7.70 (d, 2H), 1.74 (s, 9H), 1.64 (s, 9H), 1.55 (s, 9H).

References: [1]Patent: WO2006/63167,2006,A1 .Location in patent: Page/Page column 57.

9
[ 850568-54-6 ]
[ 890842-91-8 ]
[ 890842-92-9 ]

Yield	Reaction Conditions	Operation in experiment
78%	With potassium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; water; at 80℃; for 1.5h;	e) 1 ,1 -dimethylethyl 5-(6-F(N-(KI ,1-dimethylethyl)oxy1carbonyl)-beta-alanyl)amino1-3- pyridinyl)-3-(4-(r(1 ,1 -dimethylethyl)oxy\|carbonyl)phenyl)-1 H-pyrrolor2,3-blpyridine-1 - carboxylateA solution of 1 ,1 -dimethylethyl 3-bromo-5-{6-[(N-[(1 ,1-dimethylethyl)oxy]carbonyl}-beta- alanyl)amino]-3-pyridinyl}-1 H-pyrrolo[2,3-b]pyridine-1-carboxylate (95 mg, 0.2 mmol), 4-t- butoxycarbonylphenyl boronic acid (56 mg, 0.25 mmol), K2CO3 (97 mg, 0.7 mmol) and bis(diphenylphosphino)ferrocene]dichloropalladium(ll) (50 mg) in dioxane (20 ml_) and H2O (4 ml_) was heated at 80 0C for 90 minutes. The reaction was diluted with H2O and extracted with Et2O. The extracts were washed with H2O, dried and the solvent evaporated. The residue was purified by ISCO chromatography (12g silica column, 25percent EtOAc/hexane for 10 minutes, then grading to 50percent EtOAc/hexane over 1 minute, then 50percent EtOAc/hexane for 25 minutes) and afforded the titled compound 96 mg (78percent). 1H NMR (400 MHz, CDCI3) delta 8.76 (s, 1 H), 8.56 (s, 1 H), 8.34 (m, 2H), 8.28 (s, 1 H), 8.16 (m, 2H), 7.99(m, 1 H), 7.90 (s, 1 H), 7.70 (d, 1 H), 5.24 (s, 1 H), 3.54 (m, 2H), 2.71 (m, 2H), 1.74 (s, 9HO, 1.65 (s, 9H), 1.45 (s, 9H).

References: [1]Patent: WO2006/63167,2006,A1 .Location in patent: Page/Page column 59.

10
[ 850568-54-6 ]
[ 7752-82-1 ]
[ 1029715-16-9 ]

Yield	Reaction Conditions	Operation in experiment
86.6%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 120℃; for 3h;	Sodium carbonate (0.636 g, 6.0 mmol) in water (2.0 mL) was added to a mixture of 5- bromopyrimidin-2-amine (0.348 g, 2.0 mmol), <strong>[850568-54-6][4-(tert-butoxycarbonyl)phenyl]boronic acid</strong> (0.533 g, 2.4 mmol) and tetrakis(triphenylphosphine)palladium (69 mg, 0.06 mmol) in ethanol (3 mL) and toluene (3 mL). The mixture was heated at 120 0C for 3 h. After cooling to RT, the mixture was diluted with EtOAc and washed with water and brine. The organic layer was dried over Na2SOzI, filtered and concentrated under reduced pressure to afford the desired product (470 mg, 86.6percent) which was directly used in next step. LCMS: (M+H) = 272.1.

References: [1]Patent: WO2008/64157,2008,A1 .Location in patent: Page/Page column 60-61.

11
[ 850568-54-6 ]
[ 942152-80-9 ]
[ 1073129-53-9 ]

Yield	Reaction Conditions	Operation in experiment
	With cesium fluoride;tetrakis(triphenylphosphine) palladium(0); In methanol; at 80℃; for 2h;	(a) Methyl 7-(4-(tert-butoxycarbonyl)phenyl)-4-hydroxy-1- methyl-2-oxo-1,2-dihydroquinoline-3-carboxylate. To a mixture of methyl 7- bromo-4-hydroxy-1-methyl-2-oxo-1,2-dihydroquinoline-3-carboxylate (Method 7)(3.82 g, 12.2 mmol), <strong>[850568-54-6]4-(tert-butoxycarbonyl)phenylboronic acid</strong> (2.72 g, 12.2 mmol), cesium fluoride (5.58 g, 36.7 mmol), and tetrakis(triphenylphosphine)palladium [0] (0.424 g, 0.367 mmol) in a vial, was added MeOH (61 mL). The vial was sealed and heated at 80°C for 2 hours. The reaction mixture was then cooled, diluted with 200 mL of EtOAc, added to a separatory funnel, partitioned with sodium bicarbonate (saturated, aqueous), washed 2 times with 75 mL of sodium bicarbonate (saturated, aqueous), separated, dried over sodium sulfate, and concentrated via rotary evaporation to give the product. The resulting product was purified via flash chromatography (silica gel) to provide the title compound as an off-white solid.

References: [1]Patent: WO2008/130600,2008,A2 .Location in patent: Page/Page column 51.

12
[ 850568-54-6 ]
[ 37159-60-7 ]
[ 1101173-96-9 ]

Yield	Reaction Conditions	Operation in experiment
	With cesium fluoride;bis(tri-tert-butylphosphine)palladium(0); In 1,4-dioxane; at 100℃; for 16h;	To a mixture of <strong>[850568-54-6]4-(tert-butoxycarbonyl)phenylboronic acid</strong> (4.05 g, 17.1 mmol), cesium fluoride (5.57 g, 36.7 mmol), and Pd[P(t-Bu)3]2 (0.708 g, 1.39 mmol) was added dioxane (65 mL) and 3-bromo-5-chloro-l,2,4-thiadiazole (5.02 g, 25.2 mmol). The reaction mixture was degassed by bubbling nitrogen through the solution for 10 minutes and the solution was heated to 100°C. After 16 h, the reaction mixture was partially concentrated and diluted with EtOAc. The organic phase was washed with water (1 x), brine (1 x), dried over MgSO4, filtered, and concentrated. Purification by flash column chromatography on silica gel (eluted with 5percent to 10percent EtOAc in hexanes) gave tert-butyl 4-(3-bromo-l,2,4-thiadiazol-5- yl)phenylcarbamate.

References: [1]Patent: WO2009/9122,2009,A2 .Location in patent: Page/Page column 37.

13
[ 850568-54-6 ]
[ 955406-41-4 ]
[ 955406-40-3 ]
[ 955406-66-3 ]
[ 955406-67-4 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 60 - 80℃; for 1h;	Bring a mixture of Preparation 73 (0.66 g, 1.02 mmol), 4-t-butoxycarbonylphenylboronic acid (0.27 g, 1.23 mmol), sodium carbonate (0.33 g, 3.07 mmol) in THF (15 mL) and water (5 mL) to 60 C. To the mixture at 60 C., add Pd(PPh3)4 (0.06 g, 0.05 mmol). Raise the reaction temperature to 80 C. and stir the reaction for 1 hour. Cool the reaction, dilute with ethyl acetate and, wash with water and brine. Dry the organic layer (Na2SO4), remove the solvent in vacuo, and purify the crude product on silica gel using 100% hexane to 50% ethyl acetate in hexane to afford 0.61 g of the titled mixture. MS 672 (M+).

References: [1]Patent: US2009/111800,2009,A1 .Location in patent: Page/Page column 50.

14
[ 850568-54-6 ]
[ 3934-20-1 ]
4-(2-chloro-pyrimidin-4-yl)-benzoic acid tert-butyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With caesium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 70℃; for 18h;	4-(2-Chloro-pyrimidin-4-yl)-benzoic acid tert-butyl ester A mixture of 2,4-dichloropyrimidine (0.745 g), 4-tert butoxycarbonylphenyl boronic acid (0.83 g), palladium tetrakis triphenylphosphine (0.29 g) and caesium carbonate (1.625 g) in DME (60 ml) and water (60 ml) was heated at 70 0C for 18 h. Water and ethyl acetate were added and the organic phase was washed with 2M hydrochloric acid, saturated sodium carbonate, dried over sodium sulphate and concentrated in vacuo. Chromatography on silica (DCM, acetone, acetonitrile, ethanol, methanol gradient) gave 4-(2-chloro-pyrimidin- 4-yl)-benzoic acid tert-butyl ester (0.797 g) as a colourless solid after crystallisation from ether/hexane.1U NMR (CDCl3) 1.56 (9H, s), 8.05 (2H, d), 8.22 (IH, d), 8.29 (2H, d), 8.89 (IH, s). LC-MS: m/z (M+l-tBu)+ 235/237 (2.73 min).

References: [1]Patent: WO2009/34390,2009,A1 .Location in patent: Page/Page column 50.

15
[ 850568-54-6 ]
[ 16532-79-9 ]
[ 1146547-12-7 ]

Yield	Reaction Conditions	Operation in experiment
37%	With caesium carbonate;palladium diacetate; In N,N-dimethyl-formamide; at 90℃; for 18h;	Example 8: Synthesis of 4'-[2-(2-butoxy-5-chlorobenzoylamino)-l-methyl-ethyl]-biphenyl- 4-carboxylic acid (Compound 71); 8.27 Into a 250 mL round-bottomed flask are placed 4-bromophenyl acetonitrile (2.5 g, 12.7 mmol), (4-?-butylcarbonyl)boronic acid (2.82 g, 12.7 mmol), and palladium (II) acetate (0.25 g, 1.11 mmol). A 2 M solution Of Cs2CO3 (10.5 mL) is added to the flask followed by DMF (50 mL) and the mixture is heated at 90 0C for 18 h. The reaction mixture is cooled, diluted with EtOAc (100 mL), and washed with water (5 x 100 mL), 2 M HCl (50 mL), and brine (100 mL). The organic layer is dried over Na2SO4, filtered, concentrated to dryness, and the <n="77"/>resulting residue may be purified by flash silica gel chromatography (eluent: 15percent EtOAc in hexanes) to give 8.27 (1.25 g, 37percent) as a yellow solid.

References: [1]Patent: WO2009/52078,2009,A1 .Location in patent: Page/Page column 74-75.

16
[ 850568-54-6 ]
C₂₀H₂₁BrClNO₂ [ No CAS ]
C₃₁H₃₄ClNO₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In water; N,N-dimethyl-formamide; at 70℃;	To a solution of compound 11.42 and boronic acid 11.2 (12 mg, 0.028 mmol) in DMF (0.5 mL) is added sodium carbonate solution (2M, 0.1 mL). The mixture is degassed using N2 for 5 min before PdC12(dppf).DCM (2 mg, 0.002 mmol) is added. The mixture is then heated at 70 0C overnight and concentrated. The residue is purified by prep-TLC (33percent E-H) to give 12 mg of 11.43 as white solid.

References: [1]Patent: WO2009/52078,2009,A1 .Location in patent: Page/Page column 82.

17
[ 850568-54-6 ]
1-bromo-4-[(trans)-2-nitrocyclopropyl]benzene [ No CAS ]
C₂₀H₂₁NO₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
61%	With caesium carbonate;palladium diacetate; In N,N-dimethyl-formamide; at 80℃; for 5h;	A 2 M cesium carbonate solution (1.75 mL) is added to a solution of nitrocyclopropane trans-12.47 (345 mg, 1.43 mmol) and 4-(te?t-butoxycarbonyl)phenyl boronic acid (290 mg, 1.31 mmol) in DMF (10 mL). The mixture is degassed with three evacuation and argon backfill cycles. Palladium acetate (30 mg, 0.13 mmol) is added, and the solution is degassed again and heated to 80 0C. After 5 h, the mixture is cooled. Ethyl acetate and 1 N HCl are added, and the mixture is filtered through diatomaceous earth. The filtrate layers are separated, and the aqueous layer is extracted with ethyl acetate (2 x 30 mL). The organic layers are combined, washed with brine, dried over sodium sulfate, filtered, and concentrated at reduced pressure. The residue is flash chromatographed (Biotage 12 M silica cartridge, hexanes to 92:8 hexanes/ethyl acetate) to afford 12.48 (270 mg, 61percent) as a white solid.

References: [1]Patent: WO2009/52078,2009,A1 .Location in patent: Page/Page column 85.

18
[ 850568-54-6 ]
[ 191170-76-0 ]
[ 1146546-95-3 ]

Yield	Reaction Conditions	Operation in experiment
77%	With sodium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In water; N,N-dimethyl-formamide; at 85℃; for 18.1667h;	To a solution of the bromide obtained above (5.5 g, 16.5 mmol) and the boronic acid 1.2 (7.3 g, 33 mmol) in 50 mL of DMF is added an aq. Na2CO3 solution (2 M, 22 niL, 44 mmol). The mixture is purged with Ar2 for 10 min. PdCl2(dppf) (672 mg, 0.82 mmol) is then added. The reaction is stirred under Ar2 at 85°C for 18 h. After cooling the reaction mixture is poured into water (200 mL). The mixture then is extracted with EtOAc (50 mLx 3). The organic layer is separated and dried over Na2SO4 and concentrated in vacuo. The crude product is purified by chromatography to provide the desired product 1.3 (5.5 g, 77percent).

References: [1]Patent: WO2009/52078,2009,A1 .Location in patent: Page/Page column 63.

19
[ 850568-54-6 ]
[ 1146547-07-0 ]
[ 1146547-08-1 ]

Yield	Reaction Conditions	Operation in experiment
	With caesium carbonate;palladium diacetate; In N,N-dimethyl-formamide; at 90℃;	To a solution of bromide 7.21 (500 mg, 1.44 mmol) and boronic acid 2 (319 mg, 1.44 mmol) in DMF (10 mL) is added cesium carbonate (936 mg, 2.87 mmol) followed by palladium acetate (16 mg, 0.072 mmol). The mixture is degassed using an Ar stream and stirred at 90 0C overnight. The mixture is cooled to room temperature, filtered through diatomaceous earth, and partitioned between EtOAc, and water. The organic layer is dried over Na2SO4 and concentrated. Silica gel chromatography of the residue provides 360 mg of intermediate 7.22

References: [1]Patent: WO2009/52078,2009,A1 .Location in patent: Page/Page column 72.

20
[ 850568-54-6 ]
[ 1146547-17-2 ]
[ 1146547-18-3 ]

Yield	Reaction Conditions	Operation in experiment
22%	With caesium carbonate;palladium diacetate; In water; N,N-dimethyl-formamide; at 90℃; for 18h;	Into a 50 mL round-bottomed flask are weighed crude 10.36 (0.63 g, 2.4 mmol), (4-t- butylcarbonyl)boronic acid (0.73 g, 3.3 mmol), and palladium (II) acetate (73 mg, 0.33 mmol). A 2 M solution of Cs2CO3 (3.0 mL) is added to the flask followed by DMF (20 mL), and the mixture is heated at 90 0C for 18 h. The reaction mixture is cooled, diluted with <n="82"/>EtOAc (10 niL) and washed with water (5 x 10 niL), 2 M HCl (10 niL) and brine (10 niL). The organic layer is dried over Na2SO4, filtered, concentrated to dryness and the resulting residue is purified by trituration with MeOH to give 10.37 (0.12 g, 22percent) as an off-white solid.

References: [1]Patent: WO2009/52078,2009,A1 .Location in patent: Page/Page column 79-80.

21
[ 850568-54-6 ]
[ 20090-58-8 ]
[ 1185856-30-7 ]

Yield	Reaction Conditions	Operation in experiment
50%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; at 120℃; for 0.5h;Microwave irradiation;	Preparation of 4-(2-(1-(2,2-difluorobenzo[d][1,3]dioxol-5-yl)cyclopropanecarboxamido)-5-methylpyrimidin-4-yl)benzoic acid Step a: tert-Butyl 4-(2-amino-5-methylpyrimidin-4-yl)benzoateTo 4-chloro-5-methylpyrimidin-2-amine (150 mg, 1.04 mmol), tetrakistriphenylphosphine Palladium (0) (60 mg, 0.052 mmol) and <strong>[850568-54-6]4-(tert-butoxycarbonyl)phenylboronic acid</strong> (347 mg, 1.56 mmol), 1,2-DME (3 mL) and Na2CO3 (1.04 mL, 2 M, 2.08 mmol) were added and heated to 120° C. in a microwave reactor for 30 minutes. The reaction mixture was filtered using EtOAc and the filtrate was dried over anhydrous Na2SO4 and evaporated under reduced pressure. The crude product was purified by column chromatography on silica gel to yield tert-butyl 4-(2-amino-5-methylpyrimidin-4-yl)benzoate (149 mg, 50percent). ESI-MS m/z calc. 285.1, found 286.3 (M+1)+. Retention time 1.36 minutes.

References: [1]Patent: US2009/221597,2009,A1 .Location in patent: Page/Page column 41; 42.

22
[ 850568-54-6 ]
[ 1180009-36-2 ]
[ 1180009-48-6 ]

References: [1]Journal of Organic Chemistry,2009,vol. 74,p. 6390 - 6393.

23
[ 850568-54-6 ]
[ 1195951-39-3 ]
[ 1195951-40-6 ]

Yield	Reaction Conditions	Operation in experiment
	With pyridine; copper diacetate; In 1,2-dichloro-ethane; at 20℃; for 16h;Molecular sieve;	The product from Step 2 (167 mg, 0.43 mmol, 1 eq), 4-(terf-butoxycarbonyl) phenylboronic acid (247 mg, 1.11 mmol, 2.6 eq), Cu(OAc)2 (1 17 mg, 0.64 mmol, 1.5 eq), pyridine (71 mul_, 0.88 mmol, 2.05 eq), and 4A molecular sieves (284 mg) were combined in DCE (13 ml_). The resulting suspension was stirred at room temperature open to air for 16h. The reaction was concentrated to dryness and the residue purified via silica gel chromatography (gradient elution: 0percent to 30percent EtOAc in hexanes) to afford a mixture of the desired product and an inseparable impurity (230 mg) as a clear film. This material was used in the next step without further purification.

References: [1]Patent: WO2009/140342,2009,A1 .Location in patent: Page/Page column 110; 112.

24
[ 850568-54-6 ]
[ 1195951-57-5 ]
[ 1195951-58-6 ]

Yield	Reaction Conditions	Operation in experiment
33%	With pyridine; copper diacetate; In 1,2-dichloro-ethane; at 20℃; for 16h;Molecular sieve;	The brominated product from Step 4 (716 mg, 2.32 mmol, 1 eq), 4-(tert- butoxycarbonyl)phenylboronic acid (1.34 g, 6.03 mmol, 2.6 eq), Cu(OAc)2 (632 mg, 3.48 mmol, 1.5 eq), powdered 4 angstrom molecular sieves (1.4 g) and pyridine (0.57 mL, 7.08 mmol, 3.05 eq) were combined in 1 ,2-dichloroethane (60 mL) and stirred 16h at room temperature open to air. The reaction was concentrated to afford a residue which was subjected to silica gel chromatography (gradient elution, 0 to 15percent EtOAc in hexanes) to afford the desired product with impurities present. The residue was dissolved in diethyl ether (20 mL) and heptane (10 mL) was added. The solution was concentrated to ~ Vz the volume with a stream of nitrogen and was left to stand. White crystals formed, which were collected via filtration, washed with heptane, and dried to afford the desired product (371 mg, 33percent).

References: [1]Patent: WO2009/140342,2009,A1 .Location in patent: Page/Page column 118; 120.

25
[ 850568-54-6 ]
[ 1195951-70-2 ]
[ 1195951-71-3 ]

Yield	Reaction Conditions	Operation in experiment
	With pyridine; copper diacetate; In dichloromethane;Molecular sieve;	The product from Step 6 (90 mg, 0.21 mmol, 1 eq), 4-(tert- butoxycarbonyl)phenylboronic acid (120 mg, 0.53 mmol, 2.5 eq), pyridine (82 mg, 1.05 mmol, 5 eq), Cu(OAc)2 (57 mg, 0.31 mmol, 1.5 eq) and 4 angstrom molecular sieves (200 mg) were combined in dichloromethane (2 ml_) and stirred overnight. Diethyl ether (20 ml_) was added, and the mixture was filtered through Celite. The resulting filtrate was evaporated to afford a crude residue which was purified via preparative thin layer silica gel chromatography (20cmX20cm, 1000 mum, developed with 10percent EtOAc in hexanes) to afford the desired product (53 mg).

References: [1]Patent: WO2009/140342,2009,A1 .Location in patent: Page/Page column 124; 126-127.

26
[ 850568-54-6 ]
[ 915759-45-4 ]
C₂₉H₃₁F₃N₂O₆S₂ [ No CAS ]

References: [1]Bioorganic and Medicinal Chemistry,2010,vol. 18,p. 190 - 201.

27
[ 850568-54-6 ]
[ 624-28-2 ]
[ 1258878-92-0 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In methanol; toluene; at 120℃; for 0.333333h;Microwave irradiation;	Preparation of Intermediate E - Tert-butyl 4-(S-bromopgammaridiit-2-gammaI) benzoate (E-I)A mixture of 2,5-dibromopyridine (12.6 mmol), [4-(tert-butoxycarbonyl) phenyl] boronic acid (13.93 mmol), 2 N sodium carbonate (9.5 ml), methanol (20.0 ml), toluene (40.0 ml) and Tetrakis (0.63 mmol) was irradiated in the Advancer Biotage Microwave Reactor for 20 min at 120 0C. The solvent was evaporated under reduced pressure and the resulting solid diluted with methylene chloride and water. The layers were separated and the aqueous layer washed with methylene chloride. The combined organic layers was dried (MgSCU) and filtered through celite. Silica gel chromatography purification, eluting with 0 to 10 percent ethyl acetate / hexane afforded the title compound E-1. 1H NMR(CDCB): delta = 8.79 (d, J= 2.2 Hz, 1H), 8.109 (d, J= 12 Hz5 2H), 8.043 (d, J- 11.9 Hz5 2H), 7.92 (d, J= 10.9 Hz, 1H), 7.690 (d, J= 8.4 Hz, 1H), 1.651 (s, 9H).

References: [1]Patent: WO2010/147776,2010,A1 .Location in patent: Page/Page column 68-69.

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[ 850568-54-6 ]
[ 1258879-07-0 ]
[ 1258878-86-2 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In N,N-dimethyl-formamide; at 120℃; for 0.666667h;Microwave irradiation;	Step A - tert-butyl 4'- (8-[f3-methylpgammaridin-2-yI>tnethyn-2,4-dioxo-1,3,8-triazaspiro [4.5] dec-3- gamma0biphengammal-4-carboxgammalate (8- A)A reaction of a mixture of 3-(4-bromophenyl)-8-[(3-methylpyridin-2-yl)methyl]-l53,8- triazaspiro[4.5]decane~2,4-dione (Intermediate C, 640 mg, 1.49mmol), [4-(tert- butoxycarbonyl)phenyl]boronic acid (497mg, 2.24mmol), tetrakis(triphenylphosphine)paliadium(0) (138mg, 0.12mmol), and 2N solution of potassium carbonate (1.96ml, 3.72mmol) in 14 ml of DMF was heated at 12O°C for 40 minute in a microwave. The mixture was filtered through celite and washed with MeOH. The filtrate was evaporated under reduced pressure and the residue was purified by column chromatography on silica gel, elutmg with dichloromethane/ ethyl acetate/ammonia (2M in MeOH) to give Compound 8-A as a white solid. LCMS (Method A): 1.86 min, m/z (MH)+ =527.

References: [1]Patent: WO2010/147776,2010,A1 .Location in patent: Page/Page column 64.

29
[ 850568-54-6 ]
[ 1269646-16-3 ]
[ 1269650-01-2 ]

Yield	Reaction Conditions	Operation in experiment
59%	With sodium carbonate;tris-(dibenzylideneacetone)dipalladium(0); XPhos; In 1,4-dioxane; at 90℃; for 18h;Inert atmosphere; sealed tube;	To a sealed tube was added (S)-3-(3-bromopyrazolo[l ,5-a]pyrimidin-5-yl)-4-(4-fluorophenyl)oxazolidin-2-one (Preparation A; 0.200 g, 0.530 mmol), 4-(tert- butoxycarbonyl)phenyl boronic acid (0.177 g, 0.795 mmol) and 2.0 M Na2C03 (0.795 mL, 1.59 mmol) in dioxane (1 mL). The mixture was degassed by bubbling N2 through the solution. Pd2dba3 (0.0486 g, 0.053 mmol), and dicyclohexyl(2',4',6'-triisopropylbiphenyl-2- yl)phosphine (0.0253 g, 0.053 mmol) were added and the vessel was sealed under a N2 atmosphere. The mixture was heated at 90 °C for 18 hours. The reaction mixture was cooled to ambient temperature, filtered through glass fiber filter paper, concentrated and purified on silica gel (10-100percent ether in DCM ) giving (S)-tert-butyl 4-(5-(4-(4-fhiorophenyl)-2- oxooxazolidin-3-yl)pyrazolo[l ,5-a]pyrimidin-3-yl)benzoate (0.148 g, 59percent yield).

References: [1]Patent: WO2011/29027,2011,A1 .Location in patent: Page/Page column 129.

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[ 850568-54-6 ]
[ 1338223-79-2 ]