[ CAS No. 116378-40-6 ] {[proInfo.proName]}

Name: 116378-40-6|3-Amino-5-boronobenzoic acid|98%
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SKU: A737812
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Quality Control of [ 116378-40-6 ]

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Product Details of [ 116378-40-6 ]

CAS No. :	116378-40-6	MDL No. :	MFCD02179466
Formula :	C₇H₈BNO₄	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	VVQAAMZMJNXCOP-UHFFFAOYSA-N
M.W :	180.95	Pubchem ID :	2737795
Synonyms :

Safety of [ 116378-40-6 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P264-P270-P271-P280-P301+P312-P302+P352-P304+P340-P330-P363-P501	UN#:	N/A
Hazard Statements:	H302-H312-H332	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 116378-40-6 ]

* 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 [ 116378-40-6 ]

[ 116378-40-6 ] Synthesis Path-Downstream 1~42

1
[ 463-71-8 ]
[ 116378-40-6 ]
3-Isothiocyanato-5-carboxyphenylboronic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%	With hydrogenchloride at 20℃; for 0.333333h;

Reference： [1]Ramalingam, Kondareddiar; Nowotnik, David P. [Organic Preparations and Procedures International, 1991, vol. 23, # 6, p. 729 - 734]

2
[ 101084-81-5 ]
[ 116378-40-6 ]

Yield	Reaction Conditions	Operation in experiment
97.1%	With palladium 10% on activated carbon; hydrogen; In methanol; for 6h;	The 7.5g between carboxyl phenylo boric acid (45.2mmol) by adding 25 ml of concentrated sulfuric acid, under rapid stirring state by adding 25 ml fuming nitric acid, ice water bath cooling. Stirring the reaction 15 min evacuation de-ice water bath, to continue reaction 15 min. In ice water into the reaction liquid, precipitate, filtering, washing 5 times, re-crystallization with water, to obtain white solid 3-nitro-5-carboxyl phenylo boric acid 6.01g, yield 63.0% ; the 1.50g3-carboxy-5-nitro-phenylboronic acid (7.1mmol), 20 ml methanol, 10% Pd/C0 . 2g by adding 50 ml in three-necked bottle, catalytic hydrogenolysis 6h. Filtered to remove palladium-carbon, the filtrate is evaporated to dryness, to obtain white powder solid 3-amino-5-carboxyl phenylo boric acid 1.25g, yield 97.1%.
71%	With hydrogen;nickel; In ethanol; for 6h;	To make desired compound, a solution of <strong>[101084-81-5]3-carboxyl-5-nitrophenylboronic acid</strong> (422 mg, 2 mmol) in absolute ethanol (5 ml) was hydrogenated in the presence of Raney Nickel (150 mg) for 6 hours. The catalyst was removed by filtration and the solvent was evaporated to dryness, then the residue was recrystallized from water to give 257 mg (71% yield) of the desired compound as a pale yellow powder
	With hydrogen;palladium on activated charcoal; In methanol; under 2068.65 Torr; for 1.5h;	3-CARBOXY-5-NITROPHENYLBORONIC acid (250 mg, 1.1 mmol) was added to a suspension of palladium on charcoal (12 mg) in methanol (15 ml) and reduced in an atmosphere of hydrogen (40 psi). After 1.5 hours, the reaction mixture was filtered over celite and the filtrate concentrated under reduced pressure. The crude (200 mg, about 1.1 mmol) was then dissolved in water (2 ml) and dioxane (1 ml). A 10 N aqueous solution of sodium hydroxide (0.33 ml, 3 eq. ) was added. To the mixture a solution of methanesulfonyl chloride (0.1 ml, 1.2 mmol, 1. 1 eq. ) in dichloromethane (1 ml) at 0C was added dropwise. The reaction mixture was then stirred at room temperature for 2 hours and acidified with a 5% citric acid aqueous solution. The product was extracted with ethyl acetate (2 x 10 ml). The combined organic layers were dried (NA2S04) and concentrated under reduced pressure. The crude (130 mg, 0.5 mmol) was then coupled with intermediate 1 (178 mg, 0.5 mmol) under the Suzuki conditions operating as described for compound 1. The product was extracted with ethyl acetate (2 X 15 ml), dried (NA2SO4) and concentrated under reduced pressure. The product was purified on a Varian Mega Bond ChemElut (SI02) eluting with CH2CLZ/METHANOL/ACETIC acid (99: 1: 0.05 V/V/V) to give compound 6 as a pale yellow solid (13 mg, 0.02 mmol, 5% yield). MS: 534 [M+H] + HPLC/MS: Gilson instrument equipped with a C18 column Zorbax SBC18 (3.5 JIM, 2.1 x 50 MM) coupled with a diode array UV detector (220 NM) and a Finnigan Aqa mass SPECTROMETER (electron spray, positive ionization). The following settings were used: flow rate: 1 ML/MIN ; column temperature: 40C ; gradient elution A/B (eluent A: 0.5% formic acid in water; eluent B: 0.5% formic acid in ACETONITRILE) ; t = 0 min. , A/B = 95: 5, t = 8 min. , A/B =5 : 95; Rt 4. 36 min.

aluminum nickel; In ethanol;

EXAMPLE 2D 3-Amino-5-carboxyphenylboronic Acid A solution of [101084-81-5]3-nitro-5-carboxyphenylboronic acid (3.3 g, 0.016 mol) in absolute ethanol (25 ml) was hydrogenated in the presence of Raney Nickel (1 g) at 50 lbs per square inch for 4 hours in a Parr shaker. The catalyst was removed by filtration and the solvent was removed on a rotary evaporator. The solid obtained was recrystallized from water. M.P. 210-12 C.

Reference： [1]Patent: CN103497211,2016,B .Location in patent: Paragraph 0189; 0190
[2]Organic Preparations and Procedures International,1991,vol. 23,p. 729 - 734
[3]Patent: WO2005/41904,2005,A2 .Location in patent: Page/Page column 272
[4]Patent: WO2004/56366,2004,A1 .Location in patent: Page/Page column 14
[5]Patent: US5183653,1993,A

Yield	Reaction Conditions	Operation in experiment
	/BRN= 3278887/;

4
[ 116378-40-6 ]
[ 5416-93-3 ]
[ 75-31-0 ]
5-(iso-propylaminocarbonyl)-N-(4'-methoxyphenylaminocarbonyl)-3-aminophenylboronic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	Multistep reaction.;

Reference： [1]Gravel, Michael; Thompson, Kim A.; Zak, Mark; Berube, Christian; Hall, Dennis G. [Journal of Organic Chemistry, 2002, vol. 67, # 1, p. 3 - 15]

5
[ 931-53-3 ]
[ 116378-40-6 ]
[ 64-19-7 ]
[ 75-31-0 ]
[ 78-84-2 ]
N-(acetyl)-N-(1'-cyclohexylaminocarbonyl-2'-methylpropane)-3-amino-5-(isopropylaminocarbonyl)phenylboronic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%	Multistep reaction.;

Reference： [1]Gravel, Michael; Thompson, Kim A.; Zak, Mark; Berube, Christian; Hall, Dennis G. [Journal of Organic Chemistry, 2002, vol. 67, # 1, p. 3 - 15]

6
[ 116378-40-6 ]
[ 810671-79-5 ]
3-amino-5-[(4-ethylcarbamoyl-phenyl)-(8-furan-3-ylmethyl-8-aza-bicyclo[3.2.1]oct-3-ylidene)-methyl]-benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1-methyl-pyrrolidin-2-one at 180℃; for 0.166667h; microwave irradiation;

Reference： [1]Coats, Steven J.; Schulz, Mark J.; Carson, John R.; Codd, Ellen E.; Hlasta, Dennis J.; Pitis, Philip M.; Stone Jr., Dennis J.; Zhang, Sui-Po; Colburn, Ray W.; Dax, Scott L. [Bioorganic and Medicinal Chemistry Letters, 2004, vol. 14, # 22, p. 5493 - 5498]

7
[ 116378-40-6 ]
[ 351002-11-4 ]
3-amino-5-(2-morpholin-4-yl-4-oxo-4H-chromen-8-yl)-benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,4-dioxane at 90℃; for 18h;

Reference： [1]Hardcastle, Ian R.; Cockcroft, Xiaoling; Curtin, Nicola J.; El-Murr, Marine Desage; Leahy, Justin J. J.; Stockley, Martin; Golding, Bernard T.; Rigoreau, Laurent; Richardson, Caroline; Smith, Graeme C. M.; Griffin, Roger J. [Journal of Medicinal Chemistry, 2005, vol. 48, # 24, p. 7829 - 7846]

8
[ 116378-40-6 ]
[ 503467-98-9 ]
3-amino-5-(2-morpholin-4-yl-4-oxo-4H-chromen-7-yl)benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
7%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,4-dioxane at 90℃; for 18h;

9
[ 116378-40-6 ]
[ 130735-60-3 ]
3-amino-5-(2-morpholin-4-yl-4-oxo-4H-chromen-6-yl)-benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,4-dioxane at 90℃; for 18h;

10
[ 116378-40-6 ]
[ 500169-22-2 ]
C₂₂H₂₀N₂O₄S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate In 1,4-dioxane at 90℃; for 18h;

Reference： [1]Hollick, Jonathan J.; Rigoreau, Laurent J. M.; Cano-Soumillac, Celine; Cockcroft, Xiaoling; Curtin, Nicola J.; Frigerio, Mark; Golding, Bernard T.; Guiard, Sophie; Hardcastle, Ian R.; Hickson, Ian; Hummersone, Marc G.; Menear, Keith A.; Martin, Niall M. B.; Matthews, Ian; Newell, David R.; Ord, Rachel; Richardson, Caroline J.; Smith, Graeme C. M.; Griffin, Roger J. [Journal of Medicinal Chemistry, 2007, vol. 50, # 8, p. 1958 - 1972]

11
[ 2689-65-8 ]
[ 116378-40-6 ]
3-amino-5-(5-formyl-furan-2-yl)-benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With potassium carbonate In ethanol; toluene at 90℃; for 19h;

Reference： [1]Villain-Guillot, Philippe; Gualtieri, Maxime; Bastide, Lionel; Roquet, Françoise; Martinez, Jean; Amblard, Muriel; Pugniere, Martine; Leonetti, Jean-Paul [Journal of Medicinal Chemistry, 2007, vol. 50, # 17, p. 4195 - 4204]

12
[ 25487-66-5 ]
[ 116378-40-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 53 percent / conc. H₂SO₄; fuming HNO₃ / 0.75 h / 20 °C 2: 92 percent / H₂ / Raney Ni / ethanol / 4 h / 2585.74 Torr
	Multi-step reaction with 2 steps 1: nitric acid; sulfuric acid / 0.5 h / Cooling with ice 2: palladium 10% on activated carbon; hydrogen / methanol / 6 h

Reference： [1]Ramalingam, Kondareddiar; Nowotnik, David P. [Organic Preparations and Procedures International, 1991, vol. 23, # 6, p. 729 - 734]
[2]Current Patent Assignee: OCEAN UNIVERSITY OF CHINA - CN103497211, 2016, B

13
[ 116378-40-6 ]
[ 124-63-0 ]
C₈H₁₀BNO₆S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: (3-amino-5-carboxylphenyl)boronic acid; methanesulfonyl chloride With sodium hydroxide In 1,4-dioxane; dichloromethane; water at 0 - 20℃; for 2h; Stage #2: With citric acid In 1,4-dioxane; dichloromethane; water	8 3-CARBOXY-5-NITROPHENYLBORONIC acid (250 mg, 1.1 mmol) was added to a suspension of palladium on charcoal (12 mg) in methanol (15 ml) and reduced in an atmosphere of hydrogen (40 psi). After 1.5 hours, the reaction mixture was filtered over celite and the filtrate concentrated under reduced pressure. The crude (200 mg, about 1.1 mmol) was then dissolved in water (2 ml) and dioxane (1 ml). A 10 N aqueous solution of sodium hydroxide (0.33 ml, 3 eq. ) was added. To the mixture a solution of methanesulfonyl chloride (0.1 ml, 1.2 mmol, 1. 1 eq. ) in dichloromethane (1 ml) at 0°C was added dropwise. The reaction mixture was then stirred at room temperature for 2 hours and acidified with a 5% citric acid aqueous solution. The product was extracted with ethyl acetate (2 x 10 ml). The combined organic layers were dried (NA2S04) and concentrated under reduced pressure. The crude (130 mg, 0.5 mmol) was then coupled with intermediate 1 (178 mg, 0.5 mmol) under the Suzuki conditions operating as described for compound 1. The product was extracted with ethyl acetate (2 X 15 ml), dried (NA2SO4) and concentrated under reduced pressure. The product was purified on a Varian Mega Bond ChemElut (SI02) eluting with CH2CLZ/METHANOL/ACETIC acid (99: 1: 0.05 V/V/V) to give compound 6 as a pale yellow solid (13 mg, 0.02 mmol, 5% yield). MS: 534 [M+H] + HPLC/MS: Gilson instrument equipped with a C18 column Zorbax SBC18 (3.5 JIM, 2.1 x 50 MM) coupled with a diode array UV detector (220 NM) and a Finnigan Aqa mass SPECTROMETER (electron spray, positive ionization). The following settings were used: flow rate: 1 ML/MIN ; column temperature: 40°C ; gradient elution A/B (eluent A: 0.5% formic acid in water; eluent B: 0.5% formic acid in ACETONITRILE) ; t = 0 min. , A/B = 95: 5, t = 8 min. , A/B =5 : 95; Rt 4. 36 min.

Reference： [1]Current Patent Assignee: GEFIM S.P.A. - WO2004/56366, 2004, A1 Location in patent: Page/Page column 14

14
[ 116378-40-6 ]
[ 874347-49-6 ]
[ 943238-76-4 ]

Yield	Reaction Conditions	Operation in experiment
33%	Stage #1: (3-amino-5-carboxylphenyl)boronic acid; 3-iodo-2-methoxy-benzaldehyde With potassium carbonate In dichloromethane; water at 60℃; for 6h; Stage #2: With hydrogenchloride In dichloromethane; water	2.A Part A; Under argon atmosphere, aryl bromide 3 (2.32 mmol), boronic acid 14 (2.8 mmol), phosphine ligand (0.1 mmol), palladium acetate (0.5 mmol), and potassium carbonate (9.3 mmol) were suspended in degassed water and heated with stirring at 60° C. for 8 h (K. W. Anderson and S. L. Buchwald, Ang. Chem. Int. Ed., 2005, 44, 2). The mixture was poured into DCM (40 mL) and water (20 mL), and the pH of the aqueous layer was adjusted to 3 with 2N HCl. The layers were mixed and separated, and the aqueous layer was extracted with DCM (20 mL). The organic layers were combined, washed with saturated aqueous NaCl, dried over sodium sulfate, and concentrated to a light yellow oil. Purification by silica gel chromatography (0.5% HOAc/20-40% ethyl acetate/hexanes) yielded pale yellow solid (33% yield).

Reference： [1]Current Patent Assignee: INFINITY PHARMACEUTICALS INC - US2007/155705, 2007, A1 Location in patent: Page/Page column 24-25

15
[ 958646-54-3 ]
[ 116378-40-6 ]
C₁₅H₁₅NO₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate In tetrahydrofuran; water at 65℃; for 2h;	10.B Part B; To a degassed solution of iodide 29 (1.0 g, 3.8 mmol, 1.0 eq) and boronic acid 5 (1.37 g, 7.6 mmol, 2.0 eq) in a THF/water mixture (1:5, 18 mL) was added palladium acetate (22 mg, 0.09 mmol, 0.025 eq), potassium carbonate (2.1 g, 15 mmol, 4 eq) and finally a sulfated S-Phos ligand (100 mg, 0.19 mmol, 0.050 eq) (Anderson, K. W.; et. al., Angew. Chemie 2005, 44, 2922). Under an argon atmosphere, the clear mixture was heated at 65° C. for 2 h with vigorous stirring. The reaction mixture was allowed to cool to rt and was then diluted with THF (3 mL) and acetic acid (3 mL). To this stirring mixture was added formalin solution (2.4 mL, 30 mmol, 8.0 eq) and sodium cyanoborohydride (710.0 mg, 11 mmol, 3.0 eq). After stirring for 15 min, the mixture was diluted with water (50 mL) and extracted twice with EtOAc (2×75 mL). The combined organic layers were washed with saturated aqueous sodium chloride (30 mL) and dried over sodium sulfate. Concentration in vacuo provided a pale yellow oil of 30 that was used in the subsequent reaction without further purification.

Reference： [1]Current Patent Assignee: INFINITY PHARMACEUTICALS INC - US2007/155705, 2007, A1 Location in patent: Page/Page column 30-31

16
C₂₄H₃₅IN₂O₅ [ No CAS ]
[ 116378-40-6 ]
C₃₁H₄₁N₃O₇ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate In tetrahydrofuran; water at 65℃; for 4h;	1.I Part I; To a degassed (Ar) solution of pyrrolidine 12 (190 mg, 0.34 mmol) in a THF/H2O mixture (1:1, 4 mL) was added boronic acid 13 (120 mg, 0.68 mmol), palladium acetate (12 mg, 0.05 mmol), potassium carbonate (190 mg, 1.4 mmol) and finally phosphine ligand (Anderson, K. W.; et. al., Angew. Chemie 2005, 44, 2922) (54 mg, 0.1 mmol). The reaction was heated to 65° C. After 4 h at 65° C., the reaction mixture was allowed to cool to 23° C. over the course of an hour, diluted with DCM and filtered through a pad of sand and celite. The filtrate was. then extracted using DCM (50 mL) from a pH 4 water solution (20 mL). The aqueous layer was separated and extracted with DCM (2×20 mL), the combined organic extracts were washed with brine (15 mL), dried (MgSO4), filtered and concentrated in vacuo. The crude residue was used in the subsequent reaction without further purification.

Reference： [1]Current Patent Assignee: INFINITY PHARMACEUTICALS INC - US2007/155705, 2007, A1 Location in patent: Page/Page column 23

17
[ 76-09-5 ]
[ 116378-40-6 ]
[ 1009094-73-8 ]

Yield	Reaction Conditions	Operation in experiment
	In tetrahydrofuran for 48h; Heating / reflux;	14.I.1 (3-Amino-5-carboxylphenyl)boronic acid 48 (15 g, 83 mmol, 1 eq) and pinacol (29 g, 249 mmol, 3 eq) were combined with THF (72 mL) and heated to reflux. After heating at reflux for 48 h, the reaction mixture was cooled to rt and then concentrated to an orange oil. The orange oil was dissolved in MeOH (250 mL) and the solution was cooled to 0° C. using an ice bath. Formaldehyde (67 g of a 37% solution in water, 829 mmol, 10 eq) was added followed by AcOH (30 g, 497 mmol, 6 eq) and the portion-wise addition of NaBH3CN (7.8 g, 124 mmol, 3 eq). The ice bath was removed and the reaction was allowed to warm slowly to rt. After stirring for 12 h, the reaction mixture was filtered through celite, washed with EtOAc (2×100 mL) and the combined filtrates were concentrated to an orange oil. The oil was dissolved in EtOAc (200 mL), diluted with water and the pH was adjusted to pH 10 using 6 N NaOH and then extracted with EtOAc (2×200 mL). The aqueous phase was adjusted to pH 4 using 6 N HCl and extracted with DCM (2×200 mL). The combined DCM extracts were then dried over MgSO4, filtered and concentrated to provide 11 g of 49 as an off-white solid. This material was used without further purification.

Reference： [1]Current Patent Assignee: INFINITY PHARMACEUTICALS INC - US2008/114167, 2008, A1 Location in patent: Page/Page column 122

18
[ 50-00-0 ]
[ 116378-40-6 ]
[ 1009093-68-8 ]

Yield	Reaction Conditions	Operation in experiment
31%	With sodium cyanoborohydride In methanol; water at 20℃; for 0.5h;	105.A 3-amino-5-boronobenzoic acid (1 g, 5.5 mmol) was dissolved in 25 ml MeOH and 412 uL of a 37% solution of formaldehyde was added (0.166 mg, 5.5 mmol, 1 eq). Sodium cyanoborohydride (347 mg, 5.5 mmol, 1 eq) was added and the reaction stirred for 30 minutes at room temperature. The solution was dried via rotary evaporation and the resulting material was purified over silica gel (5-10% MeOH in DCM containing 0.2% acetic acid) to obtain 285 (333 mg, 31% yield). The monoalkylated product was carried on to a second reductive alkylation.

Reference： [1]Current Patent Assignee: INFINITY PHARMACEUTICALS INC - US2008/114167, 2008, A1 Location in patent: Page/Page column 211-212

19
[ 874347-53-2 ]
[ 116378-40-6 ]
[ 1009094-64-7 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium acetate; caesium carbonate In dimethyl sulfoxide at 60℃; for 36h;	1.G A flask containing aryl iodide 9 (2.0 g, 3.5 mmol, 1 eq), 3-amino-5-carboxyphenylboronic acid (1.2 g, 7.0 mmol, 2 eq), cesium carbonate (3.5 g, 10 mmol, 3 eq), potassium acetate (300 mg, 3.5 mmol, 1 eq) and Pd(dppf)Cl2 (300 mg, 0.35 mmol, 0.1 eq) was purged with argon and DMSO (35 mL) added. The mixture was heated at 60° C. for 18 h, then additional Pd(dppf)Cl2 (300 mg, 0.35 mmol, 0.1 eq) was added and heating continued for an additional 18 h. The reaction mixture was added to water (300 mL), acidified with 6 N HCl until the aqueous layer attained a pH of 4, and extracted with DCM (3×100 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo to afford a brown oil.

Reference： [1]Current Patent Assignee: INFINITY PHARMACEUTICALS INC - US2008/114167, 2008, A1 Location in patent: Page/Page column 111

20
[ 1009092-80-1 ]
[ 116378-40-6 ]
[ 1009094-75-0 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium acetate; caesium carbonate In dimethyl sulfoxide	61.G A flask containing bromide 122 (360 mg, 662 μmol, 1 eq), 3-amino-5-carboxyphenylboronic acid (240 mg, 1.32 mmol, 2 eq), cesium carbonate (383 mg, 1.99 mmol, 3 eq), potassium acetate (65 mg, 662 μmol, 1 eq) and Pd(dppf)Cl2 (48 mg, 66 μmol, 0.1 eq) was purged with argon and DMSO (5 mL) was added. The reaction mixture was added to water (300 mL), acidified with 6M HCl until the aqueous layer attained a pH of 4, and extracted with DCM (3×100 mL). The combined organic layers were washed with water (1×100 mL) dried over Na2SO4 and concentrated to a brown oil. This crude oil was dissolved in MeOH (10 mL) and treated with HOAc (38 μL, 662 μmol, 1 eq), 37% formalin (493 μL, 6.62 mol, 10 eq) and sodium cyanoborohydride (333 mg, 5.29 mmol, 8 eq). After stirring at rt for 40 min, the reaction mixture was partitioned between water (50 mL) and DCM (20 mL) and acidified with 6M HCl until the aqueous layer attained a pH of 4. The layers were separated and the aqueous extracted with DCM (3×20 mL). The combined organic layers were washed with water (1×), dried over Na2SO4, and concentrated to a brown oil. This oil was purified by silica gel flash chromatography (DCM/MeOH/AcOH 90:10:1 in DCM 0% to 100%) to give 119 mg 123 as a brown solid. Yield 29%.

Reference： [1]Current Patent Assignee: INFINITY PHARMACEUTICALS INC - US2008/114167, 2008, A1 Location in patent: Page/Page column 147

21
[ 1009093-38-2 ]
[ 116378-40-6 ]
[ 1009094-76-1 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium acetate; caesium carbonate In dimethyl sulfoxide at 60℃; for 24h;	74.I A flask containing iodide 191 (659 mg, 1.09 mmol, 1 eq), 3-amino-5-carboxyphenylboronic acid (240 mg, 2.17 mmol, 2 eq), cesium carbonate (628 mg, 3.25 mmol, 3 eq), potassium acetate (107 mg, 1.09 μmol, 1 eq) and Pd(dppf)Cl2 (79 mg, 109 μmol, 0.1 eq) was purged with argon and DMSO (5 mL) was added. The reaction was heated at 60° C. for 24 h. The reaction mixture was added to water (100 mL), acidified with 6M HCl until the aqueous layer attained a pH of 4, and extracted with DCM (3×50 mL). The combined organic layers were washed with water (1×50 mL) dried over Na2SO4 and concentrated to a brown oil. This crude oil was dissolved in MeOH (10 mL) and treated with 37% formalin (162 μL, 2.17 mol, 2 eq) and sodium cyanoborohydride (205 mg, 3.25 mmol, 3 eq). After stirring at room temperature for 30 min, the reaction mixture was quenched with sat NaHCO3 (4 mL) and partitioned between water (50 mL) and DCM (20 mL). The aqueous layer was acidified to pH 4 with 6M HCl. The layers were separated and the aqueous extracted with DCM (3×20 mL). The combined organic layers were washed with water (1×20), dried over Na2SO4, and concentrated to a brown oil which was used without purification in the next reaction.

Reference： [1]Current Patent Assignee: INFINITY PHARMACEUTICALS INC - US2008/114167, 2008, A1 Location in patent: Page/Page column 174

22
[ 1009091-87-5 ]
[ 116378-40-6 ]
[ 1009094-67-0 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium acetate; caesium carbonate In dimethyl sulfoxide at 60℃; for 4.5h;	4.G A flask containing aryl bromide 22 (90 mg, 0.17 mmol, 1 eq), 3-amino-5-carboxyphenylboronic acid (60 mg, 0.33 mmol, 2 eq), cesium carbonate (160 mg, 0.50 mmol, 3 eq), potassium acetate (15 mg, 0.17 mmol, 1 eq) and Pd(dppf)Cl2 (15 mg, 0.017 mmol, 0.1 eq) was purged with argon and DMSO (8 mL) added. The mixture was heated at 60° C. for 3 h, then additional Pd(dppf)Cl2 (15 mg, 0.17 mmol, 1 eq) was added and heating continued for 1.5 h. The reaction mixture was partitioned between water (50 mL) and DCM (50 mL) and acidified to pH 4 with 6 M HCl. The layers were separated and the aqueous extracted with DCM (3×25 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo to a brown oil. The crude oil was dissolved in MeOH (6 mL) and treated with AcOH (30 uL), 37% formalin (50 uL, 0.67 mmol, 4 eq) and NaBH3CN (30 mg, 0.50 mmol, 3 eq). After stirring at rt overnight, the reaction mixture was partitioned between water (40 mL) and DCM (40 mL) and acidified to pH 4 with 6 M HCl. The layers were separated and the aqueous extracted with DCM (3×20 mL). The combined organic layers were dried on Na2SO4, filtered and concentrated in vacuo to afford a brown oil. To an aliquot containing 9% of this crude oil (15 mg, 0.024 mmol, 1 eq) in DMF (1 mL) was added (S)-N1,N1-dimethyl-3-phenylpropane-1,2-diamine (15 uL, 0.07 mmol, 3 eq) and HBTU (30 mg, 0.07 mmol, 3 eq). The mixture was diluted with MeOH (1 mL) and purified by reverse-phase HPLC (MeCN/water with 40 mM NH4HCO3) to give 3 mg of compound 15 as a white solid. Yield 16%. MS (ESI(+)) m/z 393.25 (M+2H)2+.

Reference： [1]Current Patent Assignee: INFINITY PHARMACEUTICALS INC - US2008/114167, 2008, A1 Location in patent: Page/Page column 115-116

23
[ 1009091-97-7 ]
[ 116378-40-6 ]
[ 1009094-70-5 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium acetate; caesium carbonate In dimethyl sulfoxide at 60℃; for 4.5h;	8.G A flask containing aryl bromide 32 (90 mg, 0.16 mmol, 1 eq), 3-amino-5-carboxyphenylboronic acid (60 mg, 0.33 mmol, 2 eq), cesium carbonate (160 mg, 0.5 mmol, 3 eq), potassium acetate (15 mg, 0.17 mmol, 1 eq) and Pd(dppf)Cl2 (15 mg, 0.017 mmol, 0.1 eq) was purged with argon and DMSO (5 mL) added. The mixture was heated at 60° C. for 3 h, then additional Pd(dppf)Cl2 (15 mg, 0.17 mmol, 1 eq) was added and heating continued for 1.5 h. The reaction mixture was partitioned between water (50 mL) and DCM (50 mL) and acidified to a pH 4 with 6 N HCl. The layers were separated and the aqueous phase was extracted with DCM (3×25 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo to afford a brown oil. This crude oil was dissolved in MeOH (6 mL) and treated with AcOH (30 uL), 37% formalin (50 uL, 0.67 mmol, 4 eq) and NaBH3CN (32 mg, 0.50 mmol, 3 eq). After stirring at rt for 2 h, the reaction mixture was partitioned between water (40 mL) and DCM (40 mL) and acidified with 6 N HCl until the aqueous layer attained a pH of 4. The layers were separated and the aqueous extracted with DCM (3×20 mL). The combined organic layers were dried over Na2SO4 and concentrated in vacuo to afford a brown oil. To an aliquot containing 12% of this crude oil (20 mg, 0.031 mmol, 1 eq) in DMF (1 mL) was added (S)-N1,N1-dimethyl-3-phenylpropane-1,2-diamine (20 uL, 0.09 mmol, 3 eq) and HBTU (30 mg, 0.07 mmol, 3 eq). After stirring for 12 h, the mixture was diluted with MeOH (1 mL) and purified by reverse-phase HPLC (MeCN/water with 40 mM NH5CO2) to give 3 mg of compound 26 as a white solid. Yield 12%. MS (ESI(+)) m/z 406.26 (M+2H)2+.

Reference： [1]Current Patent Assignee: INFINITY PHARMACEUTICALS INC - US2008/114167, 2008, A1 Location in patent: Page/Page column 118

24
[ 116378-40-6 ]
[ 393-52-2 ]
[ 827299-98-9 ]

Yield	Reaction Conditions	Operation in experiment
62%	With sodium hydrogencarbonate In diethyl ether; water at 0 - 20℃;	1.4 General Procedure D: Synthesis of amide of boronoanilines To an ice-cold solution of D-1 (0.5 mmol) and NaHCOs (105 mg, 1.25 mmol) in 10 mL of water and 10 mL of ether was add dropwise D-2 (0.5 mmol) over a period of 30 min. The reaction mixture was kept at 0°C for lh and then stirred at room temperature overnight. It was then extracted twice with 10 mL of ethyl ether. The aqueous solution was acidified with 1N aqueous HCl and extracted twice with 10 mL of ethyl acetate. The combined organic layers were washed with water, and saturated brine solution, dried (NaaSOa) and concentrated. The residue was recrystallized from ethyl acetate/hexane. The product yielded is D-3. 3-(2-Fluorobenzamido)-5-carboxylphenylboronic acid (Compound FL-083) 2-Fluorobenzoyl chloride (60µL, 0.5 mmol) and 3-amino-5-carboxylphenylboronic acid (91 mg, 0.5 mmol) were reacted according to general procedure D, to give 94 mg (62% yield) of the desired compound as a white powder

Reference： [1]Current Patent Assignee: THE JOHNS HOPKINS UNIVERSITY - WO2005/41904, 2005, A2 Location in patent: Page/Page column 268

25
[ 912844-81-6 ]
[ 116378-40-6 ]
[ 1071444-78-4 ]

Yield	Reaction Conditions	Operation in experiment
	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,4-dioxane Reflux;

Reference： [1]Location in patent: body text Murr, Marine Desage-El; Cano, Celine; Golding, Bernard T.; Hardcastle, Ian R.; Hummersome, Marc; Frigerio, Mark; Curtin, Nicola J.; Menear, Keith; Richardson, Caroline; Smith, Graeme C.M.; Griffin, Roger J. [Bioorganic and Medicinal Chemistry Letters, 2008, vol. 18, # 17, p. 4885 - 4890]

26
[ 116378-40-6 ]
[ 1009094-16-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: sodium cyanoborohydride / methanol; water / 0.5 h / 20 °C 2: sodium cyanoborohydride / methanol / 1.5 h / 20 °C