191171-55-8

Basic information

• Product Name: 2-Aminophenylboronic acid pinacol ester
• Synonyms: 2-(4,4,5,5-TETRAMETHYL-1,3,2-DIOXABOROLAN-2-YL)ANILINE;2-AMINOPHENYLBORONIC ACID, PINACOL CYCLIC ESTER;2-AMINOPHENYLBORONIC ACID, PINACOL ESTER;2-AMINOBENZENEBORONIC ACID PINACOL ESTER;2-Aminobenzeneboronic acid pinacol cyclic ester;2-Aminophenylboronic acid pinacol cyclic ester~2-(2-Aminophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane;2-(2-Aminophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane;2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-
• CAS NO: 191171-55-8
• Molecular Formula: C₁₂H₁₈BNO₂
• Molecular Weight: 219.09
• Product Categories: Amines;blocks;BoronicAcids;Substituted Boronic Acids;Boronic acids;Boronic Acid
• Mol File: 191171-55-8.mol
• Article Data: 60

Chemical Properties

• Melting Point: 63-68 °C(lit.)
• Boiling Point: 125°C/1.5mmHg(lit.)
• Flash Point: 156.8 °C
• Appearance: Cream/Crystalline Powder
• Density: 1.05 g/cm³
• Vapor Pressure: 0.000118mmHg at 25°C
• Refractive Index: 1.516
• Storage Temp.: Refrigerator (+4°C)
• Solubility: Chloroform (Slightly), Methanol (Slightly)
• PKA: 3.51±0.10(Predicted)
• Water Solubility: Insoluble
• Sensitive: Air Sensitive
• BRN: 8548809
• CAS DataBase Reference: 2-Aminophenylboronic acid pinacol ester(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Aminophenylboronic acid pinacol ester(191171-55-8)
• EPA Substance Registry System: 2-Aminophenylboronic acid pinacol ester(191171-55-8)

Safety Data

• Hazard Codes: Xi,Xn
• Statements: 36/37/38-20/21/22
• Safety Statements: 26-36
• WGK Germany: 3
• Hazardous Substances Data: 191171-55-8(Hazardous Substances Data)

Usage

Chemical Properties

cream crystalline powder

Uses

Different sources of media describe the Uses of 191171-55-8 differently. You can refer to the following data:
1. Reactant involved in synthesis of: Indolo[3,4-cd]benzazepines via Pictet-Spengler-type cyclizations Antimicrobial amphiphilic aryl peptideomimetics Pyridoquinazolines and benzo[h] naphthyridines via intramolecular electrophilic substitution reaction
2. Reactant involved in synthesis of:Indolo[3,4-cd][1]benzazepines via Pictet-Spengler-type cyclizationsAntimicrobial amphiphilic aryl peptideomimeticsPyridoquinazolines and benzo[h][1,6]naphthyridines via intramolecular electrophilic substitution reactionsThienopyridine derivativesDihydroquinolonesMethacrylamidophenylboronic acids

Reactions

2-Aminophenylboronic acid pinacol ester is a reactant involved in synthesis of: ??Indolo[3,4-cd] benzazepines via Pictet-Spengler-type cyclizations ??Antimicrobial amphiphilic aryl peptideomimetics ??Pyridoquinazolines and benzo[h]naphthyridines via intramolecular electrophilic substitution reactions ??Thienopyridine derivatives ??Dihydroquinolones ??Methacrylamidophenylboronic acids

InChI:InChI=1/C12H18BNO2/c1-11(2)12(3,4)16-13(15-11)9-7-5-6-8-10(9)14/h5-8H,14H2,1-4H3

Synthetic route

2-bromoaniline (615-36-1) + bis(pinacol)diborane (73183-34-3) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In N,N-dimethyl-formamide for 12h; Reflux;	98%
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); potassium acetate In dimethyl sulfoxide at 85℃; for 12h; Inert atmosphere;	87%
With tris(trimethylphosphine)nickel(II) chloride; (2,2,2-trifluoroethoxy)trimethylsilane; cesium fluoride In toluene at 100℃; for 1h; Inert atmosphere;	84%

2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)nitrobenzene (190788-59-1) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
With 5%-palladium/activated carbon; hydrogen In ethyl acetate at 80℃; for 4h; Temperature; Solvent; Inert atmosphere;	95.8%

2-iodophenylamine (615-43-0) + 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane (25015-63-8) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
With dichlorobis(chlorodi-tert-butylphosphine) palladium(II); triethylamine In toluene for 2h; Inert atmosphere; Reflux;	95%
With N(CH2CH3)3; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2 In 1,4-dioxane (Ar); addn. of triethylamine, palladium compd. and borane deriv. to dioxane soln. of aniline deriv., heating at 100°C for 5 h;	84%
With triethylamine; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride In further solvent(s) byproducts: C6H5NH2; (Ar); addn. of 2-IC6H4NH2 to suspn. of PdCl2(dppf) in 1-butyl-3-methylimidazolium tetrafluoroborate; stirring at 100°C; cooling to ambient temp., addn. of Et3N and then pinacolborane (2 equiv.); stirring at 100°C for 0.3 h; extn. with petroleum ether, removal of solvent;	60%

2-bromoaniline (615-36-1) + 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane (25015-63-8) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; triethylamine In 1,4-dioxane at 100℃; for 12h;	87%
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; triethylamine In 1,4-dioxane Inert atmosphere;	84%
With triethylamine; CyJohnPhos; palladium diacetate In 1,4-dioxane at 80℃; for 1h;	81%

2-Chloroaniline (95-51-2) + bis(pinacol)diborane (73183-34-3) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
With potassium phosphate tribasic heptahydrate; chloro(2-dicyclohexylphosphino-2’,4’,6’-triisopropyl-1,1‘-biphenyl)[2-(2’-amino-1,1‘-biphenyl’)]palladium(II); XPhos In ethanol at 20℃; for 1h;	84%
With tris(trimethylphosphine)nickel(II) chloride; (2,2,2-trifluoroethoxy)trimethylsilane; cesium fluoride In tetrahydrofuran at 100℃; for 12h; Inert atmosphere;	80%
With (2,2,2-trifluoroethoxy)trimethylsilane; cesium fluoride; dichlorobis(trimethylphosphine)nickel In tetrahydrofuran at 100℃; for 12h; Inert atmosphere; Sealed tube;	80%
With C52H67ClFeNPPd; potassium acetate In 1,4-dioxane at 110℃; for 3h; Suzuki-Miyaura coupling; Inert atmosphere;	58%

2,3-dimethyl-2,3-butane diol (76-09-5) + 2-aminophenylboronic acid (5570-18-3) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
In tetrahydrofuran	76%
In tetrahydrofuran stirred under N2 overnight; evapn., chromy. (SiO2, EtOAc/toluene);	76%

2-iodophenylamine (615-43-0) + bis(pinacol)diborane (73183-34-3) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
With pyridine; C50H44CuN4OP2(1+)*F6P(1-); N-ethyl-N,N-diisopropylamine In water; acetonitrile at 20℃; for 12h; Inert atmosphere; Irradiation;	71%
With bis-(dimethylamino)methane In water; acetone; acetonitrile at -5℃; for 0.25h; UV-irradiation; Flow reactor; chemoselective reaction;	60%
With caesium carbonate In methanol for 24h; Reflux; Inert atmosphere;	37%
With pyridine; cesium fluoride In dimethyl sulfoxide at 105℃; for 2h; Inert atmosphere; Schlenk technique;	17%

2,3-dimethyl-2,3-butane diol (76-09-5) + Trimethyl borate (121-43-7) + 2-bis(trimethylsilyl)aminophenyl lithium → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
Stage #1: Trimethyl borate; 2-bis(trimethylsilyl)aminophenyl lithium In tetrahydrofuran at -70 - -60℃; Inert atmosphere; Stage #2: 2,3-dimethyl-2,3-butane diol In tetrahydrofuran; methanol at 20℃;	52%

C24H27BNO2P → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
With hydrogenchloride In octane; water at 20℃; for 24h; Inert atmosphere;	46%

2-Chloroaniline (95-51-2) + 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane (25015-63-8) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
With triethylamine; CyJohnPhos; palladium diacetate In 1,4-dioxane at 100℃; for 2h;	7%

2-iodophenylamine (615-43-0) + 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane (25015-63-8) → aniline (62-53-3) + 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
With triethylamine; 1-butyl-3-methylimidazolium Tetrafluoroborate; palladium diacetate at 100℃; for 6h; Product distribution; Further Variations:; Catalysts; reaction time;	A 33 % Chromat. B 61 % Chromat.

2-bromoaniline (615-36-1) + 4,4,5,5-tetramethyl-1,3,2-dioxaborolane → 2-anilineboronic acid pinacol ester (191171-55-8)

2-nitrophenylboronic acid (5570-19-4) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: H2 / Pd/C / ethanol 2: 76 percent / tetrahydrofuran View Scheme

phenylboronic acid (98-80-6) + polymer; monomer(s): Actitex 1500-1, modified with [BF4][4-N2C6H4CH2Cl]; 4-halogenobenzenethiol → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: HNO3; Ac2O; urea 2: H2 / Pd/C / ethanol 3: 76 percent / tetrahydrofuran View Scheme

phenylboronic acid (98-80-6) + Merrifield resin-CH2O(CH2)4S-CH2C6H4-Ph-4 → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: HNO3; Ac2O; urea 2: H2 / Pd/C / ethanol 3: 76 percent / tetrahydrofuran View Scheme

aniline (62-53-3) + 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane (25015-63-8) → 2-anilineboronic acid pinacol ester (191171-55-8) + 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)aniline (214360-73-3) + 3-aminophenylboronic acid pinacolate (210907-84-9)

Conditions	Yield
With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 3,4,7,8-Tetramethyl-o-phenanthrolin; 1,2,3,4,5,6,7,8,9,10,11,12-dodecahydrotriphenylene In tetrahydrofuran at 80℃; for 16h; Inert atmosphere; Glovebox; regioselective reaction;

2-nitrophenyl bromide (577-19-5) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: iron; ammonium chloride / water; ethanol / 1 h / 90 °C 2: bis[1,2-bis(diphenylphosphino)ferrocene]-palladium(0); triethylamine / 1,4-dioxane / 12 h / 100 °C View Scheme

2-(bis(trimethylsilyl)amino)phenyl bromide (54807-57-7) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: n-butyllithium / tetrahydrofuran; hexane / -70 °C / Inert atmosphere 2.1: tetrahydrofuran / -70 - -60 °C / Inert atmosphere 2.2: 20 °C View Scheme

2-bromoaniline (615-36-1) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: triethylamine / tetrahydrofuran / 0 - 60 °C / Inert atmosphere 1.2: -10 - 0 °C 2.1: n-butyllithium / tetrahydrofuran; hexane / -70 °C / Inert atmosphere 3.1: tetrahydrofuran / -70 - -60 °C / Inert atmosphere 3.2: 20 °C View Scheme

aniline (62-53-3) + bis(pinacol)diborane (73183-34-3) → 2-anilineboronic acid pinacol ester (191171-55-8) + 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)aniline (214360-73-3) + 3-aminophenylboronic acid pinacolate (210907-84-9)

Conditions	Yield
With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 4,4'-di-tert-butyl-2,2'-bipyridine In tetrahydrofuran at 80℃; for 3h; regioselective reaction;

C10H13B2NO4 + bis(pinacol)diborane (73183-34-3) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
In chloroform at 20℃; for 1h; regioselective reaction;

[1,3,2]dioxaborolan-2-yl-phenyl-amine (17739-08-1) + bis(pinacol)diborane (73183-34-3) → 2-anilineboronic acid pinacol ester (191171-55-8) + 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)aniline (214360-73-3) + 3-aminophenylboronic acid pinacolate (210907-84-9)

Conditions	Yield
With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; triethylamine; 4,4'-di-tert-butyl-2,2'-bipyridine In tetrahydrofuran at 80℃; for 3h; regioselective reaction;

C14H21B2NO4 + bis(pinacol)diborane (73183-34-3) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
In chloroform at 20℃; for 1h; regioselective reaction;

aniline (62-53-3) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: (1,5-cyclooctadiene)(methoxy)iridium(I) dimer / tetrahydrofuran / 0.17 h / 80 °C 2: (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; triethylamine; 4,4'-di-tert-butyl-2,2'-bipyridine / tetrahydrofuran / 12 h / 80 °C 3: chloroform / 1 h / 20 °C View Scheme

aniline (62-53-3) → 2-anilineboronic acid pinacol ester (191171-55-8) + 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)aniline (214360-73-3) + 3-aminophenylboronic acid pinacolate (210907-84-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: (1,5-cyclooctadiene)(methoxy)iridium(I) dimer / tetrahydrofuran / 0.17 h / 80 °C 2: (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; triethylamine; 4,4'-di-tert-butyl-2,2'-bipyridine / tetrahydrofuran / 3 h / 80 °C View Scheme

[1,3,2]dioxaborolan-2-yl-phenyl-amine (17739-08-1) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; triethylamine; 4,4'-di-tert-butyl-2,2'-bipyridine / tetrahydrofuran / 12 h / 80 °C 2: chloroform / 1 h / 20 °C View Scheme

C6H5NHBO2C2(CH3)4 (857402-61-0) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; triethylamine; 4,4'-di-tert-butyl-2,2'-bipyridine / tetrahydrofuran / 3 h / 80 °C 2: chloroform / 1 h / 20 °C View Scheme

nitrobenzene (98-95-3) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: boron trichloride; tris(pentafluorophenyl)borate / 1,2-dichloro-ethane / 6 h / -10 - 50 °C / Inert atmosphere; Sealed tube 2: triethylamine / 1,2-dichloro-ethane / 3 h / 40 °C / pH < 7 3: 5%-palladium/activated carbon; hydrogen / ethyl acetate / 4 h / 80 °C / Inert atmosphere View Scheme

(diphenylphosphino)phenylamine (6230-65-5) + 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane (25015-63-8) → 2-anilineboronic acid pinacol ester (191171-55-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2 / octane / 6 h / 150 °C / Sealed tube; Inert atmosphere 2: hydrogenchloride / octane; water / 24 h / 20 °C / Inert atmosphere View Scheme

tert-butyl 3-((5-bromothiazol-2-yl)carbamoyl)pyrrolidine-1-carboxylate + 2-anilineboronic acid pinacol ester (191171-55-8) → tert-butyl 3-((5-(2-aminophenyl)thiazol-2-yl)carbamoyl)pyrrolidine-1-carboxylate

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,4-dioxane; water at 110℃; for 24h; Inert atmosphere; Sealed tube;	100%

C16H10BrCl + 2-anilineboronic acid pinacol ester (191171-55-8) → C22H16ClN

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 100℃; for 18h;	100%

p-toluenesulfonyl chloride (98-59-9) + 2-anilineboronic acid pinacol ester (191171-55-8) → 4-methyl-N-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzenesulfonamide (796061-07-9)

Conditions	Yield
With pyridine at 0 - 25℃; for 3h;	99%
In dichloromethane for 18h; Heating;	33%

(S)-3-(1-bromovinyl)-2,2-dimethyl-1,4-dioxaspiro[4.4]nonane (1416570-55-2) + 2-anilineboronic acid pinacol ester (191171-55-8) → (R)-2-[1-(3,3-dimethyl-1,4-dioxaspiro[4.4]nonan-2-yl)vinyl]aniline (1416570-57-4)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 4h; Suzuki-Miyaura Coupling;	99%

2,5-dibromothiophen (3141-27-3) + 2-anilineboronic acid pinacol ester (191171-55-8) → 2,2′-(thiophene-2,5-diyl)dianiline

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In 1,4-dioxane; water at 100℃;	99%
With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In 1,4-dioxane for 72h; Suzuki-Miyaura Coupling; Reflux;	95%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane at 100℃; for 72h; Suzuki-Miyaura Coupling;	77%

2-(6-bromo-5-fluorobenzo[d]thiazol-2-yl)-N-(2-(cyclopropylamino)-2-oxoethyl)acetamide + 2-anilineboronic acid pinacol ester (191171-55-8) → 2-(6-(2-aminophenyl)-5-fluorobenzo[d]thiazol-2-yl)-N-(2-(cyclopropylamino)-2-oxoethyl)acetamide

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,4-dioxane at 100℃; for 1h; Inert atmosphere;	99%

3,4,5,6-tetrahydro-[1,1'-biphenyl]-2-yl trifluoromethanesulfonate (137058-15-2) + 2-anilineboronic acid pinacol ester (191171-55-8) → 3',4',5',6'-tetrahydro-[1,1':2',1''-terphenyl]-2-amine

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium hydrogencarbonate In 1,2-dimethoxyethane; water at 100℃; for 2h; Inert atmosphere;	99%

1,1-bis(diethylphosphono)ethylene (37465-31-9) + 2-anilineboronic acid pinacol ester (191171-55-8) → C16H29NO6P2 (1426661-69-9)

Conditions	Yield
With chloro(1,5-cyclooctadiene)rhodium(I) dimer In 1,4-dioxane; water at 110℃; for 6h; Inert atmosphere; Schlenk technique;	98%

2-anilineboronic acid pinacol ester (191171-55-8) + Boc-(E)-ΔAbu(β-Br)-OMe (475288-42-7) → 3-(tert-butoxycarbonyl)amino-4-methylquinolin-2-one (1036714-68-7)

Conditions	Yield
With caesium carbonate; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2 In tetrahydrofuran; water at 90℃; for 3h;	97%

methyl 2-bromo-3-cyclohexyl-1H-indole-6-carboxylate (494799-19-8) + 2-anilineboronic acid pinacol ester (191171-55-8) → 2-(2-aminophenyl)-3-cyclohexyl-1H-indole-6-carboxylic acid methyl ester (863578-19-2)

Conditions	Yield
With sodium hydrogencarbonate; tetrakis(triphenylphosphine) palladium(0) In 1,2-dimethoxyethane; water for 7h; Suzuki coupling; Heating;	96%
With sodium hydrogencarbonate; tetrakis(triphenylphosphine) palladium(0) In 1,2-dimethoxyethane; water for 9h; Heating / reflux;	96%
With sodium carbonate; bis-triphenylphosphine-palladium(II) chloride In 1,4-dioxane; water at 20 - 100℃; for 78h;	68%

3-(3-methyloxetan-3-yl)-acrylic acid ethyl ester + 2-anilineboronic acid pinacol ester (191171-55-8) → 4-(3-methyloxetan-3-yl)-3,4-dihydroquinolin-2(1H)-one

Conditions	Yield
With [Rh(OH)(cod)]2; potassium carbonate In water at 20℃; for 24h; Microwave irradiation;	96%

C12H10(2)H3F3O3S + 2-anilineboronic acid pinacol ester (191171-55-8) → C17H16(2)H3N

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium hydrogencarbonate In 1,2-dimethoxyethane; water at 100℃; for 4h; Inert atmosphere;	96%

2-bromo-3-chloro-5-(trifluoromethyl)pyridine (75806-84-7) + 2-anilineboronic acid pinacol ester (191171-55-8) → 2-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]aniline (824953-11-9)

Conditions	Yield
With water; sodium carbonate; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride In dimethyl sulfoxide for 16h;	95%

chloroacetyl chloride (79-04-9) + 2-anilineboronic acid pinacol ester (191171-55-8) → N-chloroacetyl-2-aminophenylboronic acid pinacol ester (1300115-16-5)

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃;	95%

chloroacetyl chloride (79-04-9) + 2-anilineboronic acid pinacol ester (191171-55-8) → N-chloroacetyl-2-aminophenylboronic acid pinacol ester - potassium chloride (4/1)

Conditions	Yield
With K2CO3 In acetonitrile byproducts: KCl; (inert atm.), to K2CO3 in CH3CN added dropwise under stirring 2-amino-phenylboronic acid pinacol ester, treated with 1 equiv. of chloroacetyl chloride dropwise in CH3CN, stirred at room temp. overnight; filtered, washed (CH3CN), evapd.(vac.), tritutated (pentane), dried (vac.), recrystd.;	95%

5,5-dichloro-meldrum’s acid + 2-anilineboronic acid pinacol ester (191171-55-8) → 2,2-dichloro-N-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)acetamide

Conditions	Yield
In ethyl acetate at 20℃; for 16h; Sealed tube;	95%

1-(6-(1-(4-bromo-2,6-dimethylphenylimino)ethyl)pyridin-2-yl)ethanone (896712-63-3) + 2-anilineboronic acid pinacol ester (191171-55-8) → (4-bromo-2,6-dimethylphenyl)[1-(6-(1-(2-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)phenylimino)ethyl)pyridin-2-yl)ethylidene]amine (1020072-00-7)

Conditions	Yield
In toluene byproducts: H2O; (N2/Ar, Schlenk) a soln. of amine and pyridine-compound in toluene and molecular sieves were kept at 100°C for 3 days; filtered, the solvent was rotary evapd., recrystd. from ethanol; elem. anal.;	94%

C13H7BrClNO + 2-anilineboronic acid pinacol ester (191171-55-8) → C19H13ClN2O

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 110℃; for 5h;	94%

benzalacetophenone (94-41-7) + 2-anilineboronic acid pinacol ester (191171-55-8) → 2,4-diphenylquinoline (1039-51-6)

Conditions	Yield
Stage #1: benzalacetophenone; 2-anilineboronic acid pinacol ester With potassium hydroxide; chloro(1,5-cyclooctadiene)rhodium(I) dimer In toluene at 20℃; for 24h; Inert atmosphere; Stage #2: With palladium 10% on activated carbon In toluene for 4h; Reflux; regiospecific reaction;	93%

2-chloro-5-methoxybenzaldehyde (13719-61-4) + 2-anilineboronic acid pinacol ester (191171-55-8) → 8-methoxy-phenanthridine (67342-93-2)

Conditions	Yield
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate In dimethyl sulfoxide at 120℃; for 8h; Suzuki Coupling; Inert atmosphere;	93%

3-chloro-5-(trifluoromethyl)-2-vinylpyridine + 2-anilineboronic acid pinacol ester (191171-55-8) → 3-(trifluoromethyl)-10,11-dihydro-5H-benzo[b]pyrido[2,3-f]azepine (1512812-53-1)

Conditions	Yield
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; chloro(2-dicyclohexylphosphino-2′,6′-di-i-propoxy-1,1′-biphenyl)(2′-amino-1,1′-biphenyl-2-yl)-palladium(II); potassium hydroxide; XPhos In 1,4-dioxane; water at 110℃; for 16h; Reagent/catalyst; Inert atmosphere; Sealed tube;	93%
Multi-step reaction with 2 steps 1: potassium hydroxide; [Rh(cod)OH]2 / Inert atmosphere 2: XPhos; palladium diacetate; sodium t-butanolate / 1,4-dioxane / 16 h / 110 °C / Inert atmosphere View Scheme

di(4-isocyanatophenyl)methane (101-68-8) + 2-anilineboronic acid pinacol ester (191171-55-8) → 1,1'-(methylenebis(4,1-phenylene))bis(3-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-urea)

Conditions	Yield
With triethylamine In tetrahydrofuran at 60℃; for 2h;	93%

2-bromoanisole (578-57-4) + 2-anilineboronic acid pinacol ester (191171-55-8) → 2-(2'-methoxyphenyl)aniline (1206-76-4)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 100℃; for 6h;	93%

2-bromothiophene (1003-09-4) + 2-anilineboronic acid pinacol ester (191171-55-8) → 2-(thiophen-2-yl)aniline (62532-99-4)

Conditions	Yield
Stage #1: 2-bromothiophene; tetrakis(triphenylphosphine) palladium(0) In 1,2-dimethoxyethane for 0.166667h; Stage #2: 2-anilineboronic acid pinacol ester With sodium hydrogencarbonate In 1,2-dimethoxyethane; water at 95℃; for 3h;	92%
With sodium hydrogencarbonate; tetrakis(triphenylphosphine) palladium(0) In 1,2-dimethoxyethane; water at 95℃; for 3.16667h;	92%

3,6-dibromopyridazine (17973-86-3) + 2-anilineboronic acid pinacol ester (191171-55-8) → 2-[6-(2-aminophenyl)pyridazin-3-yl]aniline (1276656-60-0)

Conditions	Yield
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate In water; N,N-dimethyl-formamide at 20 - 90℃; for 18h; Suzuki coupling; Inert atmosphere;	92%

Methyl 2-(2-iodo-1H-indol-3-yl)acetate (275361-65-4) + 2-anilineboronic acid pinacol ester (191171-55-8) → paullone (142273-18-5)

Conditions	Yield
With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; caesium carbonate; copper(l) chloride In N,N-dimethyl-formamide at 80℃; for 2h; Suzuki coupling; Inert atmosphere;	92%

2-anilineboronic acid pinacol ester (191171-55-8) + 1,4-dibromo-2,5-bis(trimethylsilyl)benzene → 2,2′-(1,4-bis(trimethylsilyl)benzene-2,5-diyl)dianiline

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium hydrogencarbonate In 1,2-dimethoxyethane; water at 90℃; for 24h; Suzuki Coupling; Schlenk technique; Inert atmosphere;	92%
With tetrakis(triphenylphosphine) palladium(0); sodium hydrogencarbonate In 1,2-dimethoxyethane at 90℃; for 24h; Suzuki-Miyaura Coupling; Schlenk technique; Inert atmosphere;	92%

Upstream product

• 95-51-2 o-chloroaniline 
• 25015-63-8 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane 
• 615-43-0 2-iodophenylamine 
• 615-36-1 2-bromoaniline 
• 73183-34-3 bis(pinacol)diborane 
• 6230-65-5 (diphenylphosphino)phenylamine 
• 98-95-3 nitrobenzene 
• 190788-59-1 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)nitrobenzene 
• 857402-61-0 N-(pinacolboryl)aniline 
• 17739-08-1 [1,3,2]dioxaborolan-2-yl-phenyl-amine 
• 62-53-3 aniline 
• 76-09-5 2,3-dimethyl-2,3-butane diol 
• 121-43-7 Trimethyl borate 
• 54807-57-7 2-(bis(trimethylsilyl)amino)phenyl bromide 

Downstream Products

• 1218790-42-1 2-N-acryloylaminophenylboronic acid pinacol ester 
• 528607-67-2 methyl (+/-)-1-(2-aminophenyl)-8-ethyl-3-formyl-5,6,7,8-tetrahydroindolizin-8-propionate 
• 29528-30-1 2-(2-pyridyl)aniline 
• 177202-83-4 2-(pyridin-3-yl)phenylamine 
• 832-68-8 6-aminophenanthridine 
• 934176-62-2 5-(2-amino-phenyl)-thiophene-2-carboxylic acid methyl ester 
• 824953-11-9 2-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]aniline 
• 1036714-65-4 3-(tert-butoxycarbonylamino)-1H-quinolin-2-one 
• 1036714-64-3 3-(tert-butoxycarbonyl)amino-4-(2-aminophenyl)quinolin-2-one 
• 23207-85-4 3-amino-1,2-dihydro-2-oxo-4-phenylquinoline 
• 1036714-70-1 Boc-(Z)-ΔPhe[β-(2-aminophenyl)]-OMe 
• 1020071-99-1 [1-(6-(1-(2-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)phenylimino)ethyl)pyridin-2-yl)ethylidene](2,4,6-trimethylphenyl)amine 
• 1020072-00-7 (4-bromo-2,6-dimethylphenyl)[1-(6-(1-(2-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)phenylimino)ethyl)pyridin-2-yl)ethylidene]amine 
• 1020071-98-0 2,6-bis[1-(2-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)phenylimino)ethyl]pyridine 

Relevant articles and documents

Self-activation and 1,8-stereoinduction in a boronate-substituted dienophile

The [4+2] cycloaddition of ortho-boronoanilide dienophile 4 with cyclopentadiene was found to proceed faster than both its para isomer 8 and the unsubstituted derivative 6, thereby confirming that self-activation by internal coordination is operative in the case of 4. Chiral boronic esters derivatives 9 and 10 provided a small level of remote 1,8-stereoinduction. These results show that dialkoxyboronic esters can operate as weak, internal Lewis acids and activate carbonyl-containing functionalities in cycloaddition reactions.

1,3,5-Tris(2′-aminophenyl)benzene: A novel platform for molecular receptors

The synthesis of a novel, rigid, aromatic platform for molecular receptors is described. 1,3,5-Tris(2′-aminophenyl)benzene was prepared via Suzuki-Miyaura cross-coupling reactions of 2-aminophenylboronic acid with 1,3,5-triiodobenzene in the presence of Ba(OH)2, Pd(OAc)2 and (2-biphenyl)dicyclohexylphosphine. Alternatively, one-pot borylation of 2-bromoaniline and cross-coupling of the resulting boronate ester with 1,3,5-triiodobenzene was investigated. Georg Thieme Verlag Stuttgart.

Enantioselective Construction of Axially Chiral Azepine-Containing P,N-Ligands from l -Alanine

A family of axially chiral azepine-containing seven-membered cyclic P,N-ligands (named Indole-azepinap) have been prepared by using l-alanine as an original chirality source. The direct chromatographic separation of two diastereomeric phosphine oxides on silica gel enabled these ligands to be easy available, allowing further structural and electronic modifications. Preliminary application of these Indole-azepinaps has been demonstrated in a Pd-catalyzed asymmetric allylic alkylation with high yields and moderate enantioselectivities.

Oxidation of Nonactivated Anilines to Generate N-Aryl Nitrenoids

A low-temperature, protecting-group-free oxidation of 2-substituted anilines has been developed to generate an electrophilic N-aryl nitrenoid intermediate that can engage in C-NAr bond formation to construct functionalized N-heterocycles. The exposure of 2-substituted anilines to PIFA and trifluoroacetic acid or 10 mol percent Sc(OTf)3 triggers nitrenoid formation, followed by productive and selective C-NAr and C-C bond formation to yield spirocyclic- or bicyclic 3H-indoles or benzazepinones. Our experiments demonstrate the breadth of these oxidative processes, uncover underlying fundamental elements that control selectivity, and demonstrate how the distinct reactivity patterns embedded in N-aryl nitrenoid reactive intermediates can enable access to functionalized 3H-indoles or benzazepinones.