1679-18-1

Usage

InChI:InChI=1/C6H6BClO2/c8-6-3-1-5(2-4-6)7(9)10/h1-4,9-10H

Synthetic route

4-chlorophenyl trifluoromethanesulfonate (29540-84-9) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
Stage #1: 4-chlorophenyl trifluoromethanesulfonate With tris(dibenzylideneacetone)dipalladium(0) chloroform complex; diisopropopylaminoborane; triethylamine; triphenylphosphine In tetrahydrofuran at 65℃; for 12h; Alcaraz-Vaultier borylation; Inert atmosphere; Stage #2: With methanol In tetrahydrofuran at 0℃; Inert atmosphere; Further stages;	97%

para-dichlorobenzene (106-46-7) + Trimethyl borate (121-43-7) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
Stage #1: para-dichlorobenzene With iodine; magnesium In tetrahydrofuran; toluene at 60 - 65℃; for 2h; Grignard Reaction; Inert atmosphere; Stage #2: Trimethyl borate In tetrahydrofuran; toluene at -20 - -15℃; for 2h; Solvent; Reagent/catalyst; Temperature;	96.2%

para-dichlorobenzene (106-46-7) + boric acid tributyl ester (688-74-4) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
Stage #1: para-dichlorobenzene With iodine; magnesium In tetrahydrofuran; toluene at 60 - 65℃; for 0.5h; Grignard Reaction; Inert atmosphere; Stage #2: boric acid tributyl ester In tetrahydrofuran; toluene at -20 - -15℃; for 2h;	95.1%

bromochlorobenzene (106-39-8) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
Stage #1: bromochlorobenzene With n-butyllithium In tetrahydrofuran; hexane Inert atmosphere; Stage #2: With Trimethyl borate In tetrahydrofuran; hexane Inert atmosphere;	90%
Stage #1: bromochlorobenzene With diisobutylaluminium hydride; magnesium; lithium chloride In tetrahydrofuran; toluene at 20℃; for 0.166667h; Inert atmosphere; Stage #2: With Trimethyl borate In tetrahydrofuran; toluene at 0℃; Inert atmosphere; Stage #3: With hydrogenchloride; water In tetrahydrofuran; toluene at 0℃; Inert atmosphere;	81%
Stage #1: bromochlorobenzene With tert.-butyl lithium In tetrahydrofuran at -78℃; Stage #2: With Trimethyl borate In tetrahydrofuran at -78 - 20℃; Further stages.;	74%

tetrahydroxydiboron (13675-18-8) + 1-Chloro-4-iodobenzene (637-87-6) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
In methanol at 15℃; for 3h; Microwave irradiation;	87%
With bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II); tetramethyl ammonium acetate In 2-methyltetrahydrofuran; methanol; water at 40℃; for 6h; Schlenk technique; Inert atmosphere;	67%
With bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II); N-ethyl-N,N-diisopropylamine In 2-methyltetrahydrofuran; methanol at 50 - 55℃; Inert atmosphere;	85 %Chromat.
With [{Pd(μ-Cl){κ2-P,C-P(iPr)2(OC6H3-2-Ph)}}2]; sodium acetate In dichloromethane; water at 40℃; for 6h; Inert atmosphere;

water (7732-18-5) + boron trichloride (10294-34-5) + chlorobenzene (108-90-7) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
Stage #1: boron trichloride; chlorobenzene With aluminum (III) chloride at 110℃; for 10h; Inert atmosphere; Stage #2: water at 0 - 5℃; pH=1 - 2; Temperature;	86.6%

water (7732-18-5) + potassium (4-chlorophenyl)trifluoroborate → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
With 1H-imidazole; iron(III) chloride at 20℃; for 0.25h; Inert atmosphere;	85%

methanol (67-56-1) + bromochlorobenzene (106-39-8) + diisopropylamine borane (55124-35-1) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
Stage #1: diisopropylamine borane With magnesium; phenylmagnesium bromide In tetrahydrofuran at 20℃; for 0.166667h; Stage #2: bromochlorobenzene In tetrahydrofuran at 70℃; Stage #3: methanol Further stages;	84%

borane (13283-31-3) + (4-chlorphenyl)magnesium bromide (873-77-8) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
With water In tetrahydrofuran slow addn. of 10 mmol of the Grignard reagent to a stirred soln. of borane in THF (40 mmol); the mixt. was poured into ice-water and acidified with 10% HCl;; extn. into ether three-times; the combined extracts were dried over NaSO4; removal of solvent under reduced pressure; trituration with petroleum ether; recrystn. from H2O;;	81%

bromochlorobenzene (106-39-8) + tetrahydroxydiboron (13675-18-8) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
In methanol at 15℃; for 4h; Microwave irradiation;	78%
With bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II); N-ethyl-N,N-diisopropylamine In 2-methyltetrahydrofuran; methanol at 50 - 55℃; Inert atmosphere;	78 %Chromat.

4-chloro-aniline (106-47-8) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
Stage #1: 4-chloro-aniline With hydrogenchloride; sodium nitrite In methanol; water at 0 - 5℃; for 0.5h; Stage #2: With tetrahydroxydiboron In methanol; water at 20℃; for 1h;	73%
Multi-step reaction with 2 steps 1.1: water / 0.03 h / 20 °C 1.2: 0.25 h / 0 °C 2.1: N,N-dimethyl-formamide / 0.25 h / 20 °C View Scheme

bromochlorobenzene (106-39-8) + tri-n-propyl borate (688-71-1) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
Stage #1: bromochlorobenzene With iodine; magnesium In tetrahydrofuran for 2h; Inert atmosphere; Reflux; Stage #2: tri-n-propyl borate In tetrahydrofuran at -78 - 20℃; Inert atmosphere; Stage #3: With hydrogenchloride In water	63%

potassium (4-chlorophenyl)trifluoroborate → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
With water; silica gel at 20℃; for 1h; Inert atmosphere;	60%

tetrahydroxydiboron (13675-18-8) + p-chlorobenzenediazonium tetrafluoroborate (673-41-6) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
In N,N-dimethyl-formamide at 20℃; for 0.25h;	60%

tetrahydroxydiboron (13675-18-8) + 4-chloro-aniline (106-47-8) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
Stage #1: 4-chloro-aniline With hydrogenchloride; sodium nitrite In water at 0℃; for 0.25h; Stage #2: tetrahydroxydiboron With sodium acetate In water at 20℃; for 0.333333h;	53%
Stage #1: 4-chloro-aniline With hydrogenchloride; sodium nitrite In water at 0℃; for 0.25h; Stage #2: tetrahydroxydiboron With potassium carbonate In water at 20℃; for 0.333333h;

bromochlorobenzene (106-39-8) + Triisopropyl borate (5419-55-6) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
Stage #1: bromochlorobenzene With n-butyllithium In tetrahydrofuran; hexane at -78 - -10℃; Stage #2: Triisopropyl borate In tetrahydrofuran; hexane at -78 - 20℃;	34%

di-(p-chlorophenyl)borinic acid (89566-59-6) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
With water; bromine
With water; chlorine

(4-chlorphenyl)magnesium bromide (873-77-8) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
With diethyl ether; boron trifluoride Zersetzen des Reaktionsprodukts mit Salzsaeure und nachfolgendes Einleiten von Wasserdampf in das entstehendene 4-Chlor-phenylbordifluorid;

1-Chloro-4-iodobenzene (637-87-6) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
(i) (UV-irradiation), BBr3, (ii) aq. NaOH; Multistep reaction;

tris(4-chlorophenyl)boroxine (7519-91-7) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
With water In chloroform-d1 at 25℃; Equilibrium constant; Thermodynamic data;

bromochlorobenzene (106-39-8) + borane (13283-31-3) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions

Yield

With water; magnesium In tetrahydrofuran a 2.0 M soln. of borane (40 mmol) in THF was added to flame dried Mg turnings (12 mmol) at 0°C; slow addn. of the aryl bromide (10 mmol)in THF; stirring at room temp. for 12-16 h; the mixt. was poured into ice-water and acidified with 10% HCl;; extn. into ether three-times; the combined extracts were dried over NaSO4; removal of solvent under reduced pressure; trituration with petroleum ether; recrystn. from H2O;;

boron trifluoride (7637-07-2) + (4-chlorphenyl)magnesium bromide (873-77-8) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
With H2=
With H2=

borane (13283-31-3) + tetra(p-chlorophenyl)tin (15799-48-1) + ethanolamine (141-43-5) → 4-Chlorophenylboronic acid (1679-18-1) + di(p-chlorophenyl)borinic acid ethanolamine complex

Conditions

Yield

With water In tetrahydrofuran; diethyl ether; ethanol to THF soln. of Sn compd. added BH3 (N2, room temp.),refluxed (1 h), added H2O,stirred (30 min),extd. (Et2O), dried (MgSO4),evapd. in vac.,heated with pentane,filtered ArB(OH)2,filtrate evapd.,added Et2O,EtOH soln. of HOCH2CH2NH2 added,refluxed (30 min); filtered hot, complex pptd. by cooling, filtered; ArB(OH)2 recrystd. from H2O; compds. identified by m. p., IR, NMR;

Trimethyl borate (121-43-7) + (4-chlorphenyl)magnesium bromide (873-77-8) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
In tetrahydrofuran dropwise addn. of p-ClC6H4MgBr to borane at -70°C; stirred below -60°C for 1 h; hydrolyzed (sulfuric acid); filtration; sepn. of org. layer; extn. of aq. layer (ether); combined org. layer washed (H2O); dried (Na2SO4); concn. of soln.; crystn.; washed (hexane, H2O); IR; NMR; mass spectra;

1,2-bis(p-chlorophenyl)diborane(6) (120208-73-3) + water (7732-18-5) → 4-Chlorophenylboronic acid (1679-18-1)

1,2-bis(p-chlorophenyl)diborane(6) (120208-73-3) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
hydrolysis;;
hydrolysis;;

2-(4-chlorophenyloxy)-2-(4-chlorophenyl)-5-methyl-3,3-tetramethylen-1-oxa-3-azonia-2-boratacyclopentane (95890-68-9) → 2-monochlorophenol (95-57-8) + 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
With water In methanol; water byproducts: 4-chlorophenol, 1-pyrrilidino-2-propanol; borate was suspended in boiling water, dild. with methanol until dissolution of the ppt.; cooled, mixt. was analyzed by TLC (SiO2, dioxane-benzene-AcOH);	A 0% B n/a

4-chlorophenylboronic dimethyl ester → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
With sodium hydrogencarbonate at 20℃; pH=6.5;
With hydrogenchloride; water Inert atmosphere;	2.07 g
With hydrogenchloride In water at 20℃; Inert atmosphere; Schlenk technique;

bromochlorobenzene (106-39-8) + bis(pinacol)diborane (73183-34-3) → 4-Chlorophenylboronic acid (1679-18-1)

Conditions	Yield
With Co(1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene)2Cl2; potassium methanolate In tert-butyl methyl ether at 70℃; for 8h;	62 %Spectr.

4-Chlorophenylboronic acid (1679-18-1) + (7-bromo-2,3-dimethoxy-quinoxalin-5-ylmethyl)-phosphonic acid diethyl ester (187479-58-9) → [7-(4-chloro-phenyl)-2,3-dimethoxy-quinoxalin-5-ylmethyl]-phosphonic acid diethyl ester

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,2-dimethoxyethane for 24h; Suzuki cpupling; Heating;	100%

4-Chlorophenylboronic acid (1679-18-1) + methyl vinyl ketone (78-94-4) → 4-(4-chlorophenyl)butan-2-one (3506-75-0)

Conditions	Yield
With potassium phosphate; chloro(1,5-cyclooctadiene)rhodium(I) dimer In 1,4-dioxane; water at 60℃; Glovebox;	100%
With cyclo-octa-1,5-diene In methanol at 65℃; for 8h; Inert atmosphere;	89%
polystyrene In water at 25℃; for 24h; Michael reaction;	79%

iodobenzene (591-50-4) + 4-Chlorophenylboronic acid (1679-18-1) → 4'-biphenyl chloride (2051-62-9)

Conditions	Yield
With 1,4-diaza-bicyclo[2.2.2]octane; potassium carbonate; palladium diacetate In acetone at 110℃; for 2h; Suzuki-Miyaura cross-coupling reaction;	100%
With potassium carbonate In ethanol at 80℃; for 12h; Reagent/catalyst; Suzuki-Miyaura Coupling;	100%
With potassium carbonate; [PS-PEG-adppp-Pd(η3-C3H5)]Cl In water at 50℃; for 12h; Suzuki-Miyaura coupling;	99%

4-bromobenzenecarbonitrile (623-00-7) + 4-Chlorophenylboronic acid (1679-18-1) → 4-(4'-chlorophenyl)benzonitrile (57774-36-4)

Conditions	Yield
With [(PdCl2)Fe{C5H4P-(OC6H3(OMe-o)(C3H5-p))2}2]; potassium carbonate In methanol at 60℃; for 3.5h; Catalytic behavior; Inert atmosphere; Schlenk technique;	100%
Stage #1: 4-bromobenzenecarbonitrile In N,N-dimethyl-formamide at 90℃; for 0.833333h; Microwave irradiation; Stage #2: 4-Chlorophenylboronic acid With potassium carbonate In N,N-dimethyl-formamide at 102℃; for 1h; Suzuki-Miyaura Coupling; Microwave irradiation;	99%
With dichloro bis(acetonitrile) palladium(II); C95H120N20O10(10+)*10F6P(1-); potassium carbonate In ethanol at 50℃; for 1.5h; Suzuki-Miyaura Coupling;	96%

2-bromo-pyridine (109-04-6) + 4-Chlorophenylboronic acid (1679-18-1) → 2-(4-chlorophenyl)pyridine (5969-83-5)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene for 18h; Inert atmosphere; Reflux;	100%
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In 1,4-dioxane; water at 120℃; Inert atmosphere;	99%
With sodium phosphate; palladium on activated charcoal In isopropyl alcohol at 80℃; for 24h; Suzuki-Miyaura coupling reaction;	95%

4-Chlorophenylboronic acid (1679-18-1) + 4-chlorobenzonitrile (100-00-5) → 4-(4-nitrophenyl)chlorobenzene (6242-97-3)

Conditions	Yield
With potassium carbonate; Pd(OAc)2*(1,1,3,3-tetramethyl-2-n-butylguanidine)2 In ethanol; water at 20℃; for 20h; Suzuki cross-coupling;	100%
With C20H16Cl2N2Pd; potassium carbonate In N,N-dimethyl-formamide at 100℃; for 6h; Suzuki-Miyaura Coupling;	91%
With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 5h; Catalytic behavior; Suzuki-Miyaura Coupling;	89%

(S)-2-((5-bromopyridin-3-yloxy)methyl)pyrrolidine-1-carboxylic acid tert-butyl ester (191162-30-8) + Pd(0) + 4-Chlorophenylboronic acid (1679-18-1) → 5-(4-chlorophenyl)-3-(2-(R)-pyrrolidinylmethoxy)pyridine

Conditions	Yield
With sodium carbonate In toluene	100%

(S)-2-((5-bromopyridin-3-yloxy)methyl)pyrrolidine-1-carboxylic acid tert-butyl ester (191162-30-8) + Pd(0) + 4-Chlorophenylboronic acid (1679-18-1) → 3-(1-BOC-2-(R)-Pyrrolidinylmethoxy)-5-(4-chlorophenyl)pyridine (299893-21-3)

Conditions	Yield
With sodium carbonate In toluene	100%

(S)-2-((5-bromopyridin-3-yloxy)methyl)pyrrolidine-1-carboxylic acid tert-butyl ester (191162-30-8) + Pd(0) + 4-Chlorophenylboronic acid (1679-18-1) + sodium carbonate (497-19-8) → 5-(4-chlorophenyl)-3-(2-(R)-pyrrolidinylmethoxy)pyridine

Conditions	Yield
In toluene	100%
In toluene	100%

(S)-2-((5-bromopyridin-3-yloxy)methyl)pyrrolidine-1-carboxylic acid tert-butyl ester (191162-30-8) + Pd(0) + 4-Chlorophenylboronic acid (1679-18-1) + sodium carbonate (497-19-8) → 3-(1-BOC-2-(R)-Pyrrolidinylmethoxy)-5-(4-chlorophenyl)pyridine (299893-21-3)

Conditions	Yield
In toluene	100%

2-(5-amino-2-oxobenzo[d]oxazol-3(2H)-yl)-N-methyl-N-phenylacetamide + 4-Chlorophenylboronic acid (1679-18-1) → 2-[5-[(4-chlorophenyl)amino]-2-oxo-1,3-benzoxazol-3(2H)-yl]-N-methyl-N-phenylacetamide

Conditions	Yield
With triethylamine; copper diacetate In dichloromethane at 20 - 25℃; for 15h;	100%

3-Bromopyridine (626-55-1) + 4-Chlorophenylboronic acid (1679-18-1) → 4-(3'-pyridinyl)-1-chlorobenzene (5957-97-1)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 75℃; for 24h; Inert atmosphere; Reflux;	100%
With potassium carbonate In isopropyl alcohol at 85 - 90℃; for 24h; Suzuki-Miyaura Coupling;	94%
With potassium phosphate tribasic heptahydrate; C18H24N3O2Pd In ethanol; water at 60℃; for 4h; Suzuki-Miyaura Coupling;	88%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene for 24h; Suzuki-Miyaura coupling; Inert atmosphere; Reflux;	86%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene

4-Chlorophenylboronic acid (1679-18-1) + 4,4'-dithiobis [5-amino-3-cyano-1-{2,6-dichloro-4-(trifluoromethyl)phenyl}-1H-pyrazole] (130755-46-3) → 5-amino-4-[(4-chlorophenyl)thio]-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carbonitrile (1158997-68-2)

Conditions	Yield
With copper(l) iodide; 1,10-Phenanthroline; oxygen In water; dimethyl sulfoxide at 100℃; for 24h;	100%

(2-nitroethenyl)benzene (102-96-5) + 4-Chlorophenylboronic acid (1679-18-1) → (R)-1-chloro-4-(2-nitro-1-phenylethyl)benzene (1245819-33-3)

Conditions	Yield
With heterogeneous Rh/Ag bimetallic nanoparticle catalyst immobilized on chiral polymer In water; toluene at 100℃; for 24h; Inert atmosphere; enantioselective reaction;	100%
With potassium hydrogen difluoride; C60H52Cl2Rh2 In water; toluene at 50℃; for 51h; Inert atmosphere; enantioselective reaction;	94%
With chlorobis(ethylene)rhodium(I) dimer; potassium hydrogen bifluoride; C28H22 In water; toluene at 100℃; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	92%
With chlorobis(ethylene)rhodium(I) dimer; C17H27NO In water; toluene at 100℃; for 16h; Reagent/catalyst; Inert atmosphere; enantioselective reaction;	87 %Chromat.

6-chloro-4-iodo-5-(2,2,2-trifluoroethoxy)-2-pyridinemethanol (1364676-94-7) + 4-Chlorophenylboronic acid (1679-18-1) → 6-chloro-4-(4-chlorophenyl)-5-(2,2,2-trifluoroethoxy)-2-pyridinemethanol (1364676-96-9)

Conditions	Yield
With sodium carbonate; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2 In water; toluene at 90℃; for 1.5h; Inert atmosphere;	100%
With sodium carbonate; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2 In toluene at 90℃; for 1.5h; Inert atmosphere;	100%
With sodium carbonate; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2 In toluene at 90℃; for 1.5h; Inert atmosphere;	100%
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate In toluene at 90℃; for 1.5h; Inert atmosphere;	100%

5-bromo-6-cyclobutyloxy-3-pyridinecarboxylic acid (1364678-46-5) + 4-Chlorophenylboronic acid (1679-18-1) → 5-(4-chlorophenyl)-6-(cyclobutyloxy)-3-pyridinecarboxylic acid (1364678-51-2)

Conditions	Yield
With potassium carbonate; tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran; water at 100℃;	100%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,2-dimethoxyethane; ethanol; water at 85℃; for 3.5h; Inert atmosphere;	89%
Stage #1: 5-bromo-6-cyclobutyloxy-3-pyridinecarboxylic acid; 4-Chlorophenylboronic acid With potassium carbonate; tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran; water at 100℃; Stage #2: In water; ethyl acetate pH=2;

2-(3-bromophenyl)-N-methoxy-N-methylacetamide (866270-03-3) + 4-Chlorophenylboronic acid (1679-18-1) → 2-(4'-chloro-3-biphenylyl)-N-methoxy-N-methylacetamide (1365177-17-8)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,2-dimethoxyethane; water at 90℃; for 5h; Inert atmosphere;	100%

[4-bromo-6-chloro-5-(2,2,2-trifluoro-ethoxy)-pyridin-2-yl]-methanol (1382465-52-2) + 4-Chlorophenylboronic acid (1679-18-1) → 6-chloro-4-(4-chlorophenyl)-5-(2,2,2-trifluoroethoxy)-2-pyridinemethanol (1364676-96-9)

Conditions	Yield
With sodium carbonate; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2 In toluene at 90℃; for 1.5h; Inert atmosphere;	100%

N2-(5-bromo-2-methylphenyl)-N2-{2-[1,3-dihydro-2H-isoindol-2-yl(methyl)amino]-2-oxoethyl}-N1-{2-[(tert-butoxycarbonyl)(isopropyl)amino]ethyl}glycinamide + 4-Chlorophenylboronic acid (1679-18-1) → N2-(4'-chloro-4-methylbiphenyl-3-yl)-N2-{2-[1,3-dihydro-2H-isoindol-2-yl(methyl)amino]-2-oxoethyl}-N1-{2-[(tert-butoxycarbonyl)(isopropyl)amino]ethyl}glycinamide (1190895-17-0)

Conditions	Yield
	100%

(3-amino-2,6-difluoro-phenyl)-[5-bromo-1-(2,6-dichlorobenzoyl)pyrrolo[2,3-b]pyridin-3-yl]methanone + 4-Chlorophenylboronic acid (1679-18-1) → (3-(3-amino-2,6-difluorobenzoyl)-5-(4-chlorophenyl)-1H-pyrrolo[2,3-b]pyridin-1-yl)(2,6-dichlorophenyl)methanone

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; sodium hydrogencarbonate In 2-methyltetrahydrofuran; water at 70 - 75℃; for 3h; Concentration; Temperature; Time; Inert atmosphere;	100%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate In 1,4-dioxane; water at 80 - 82℃; for 2h; Inert atmosphere;	75%
With bis-triphenylphosphine-palladium(II) chloride; sodium hydrogencarbonate In 2-methyltetrahydrofuran; water at 90℃; for 16h;

4-Chlorophenylboronic acid (1679-18-1) + 4-chloro-aniline (106-47-8) → bis(4-chlorophenyl)amine (6962-04-5)

Conditions	Yield
With 2,6-dimethylpyridine; fac-tris(2-phenylpyridinato-N,C2')iridium(III); copper diacetate; n-tetradecanoic acid In toluene; acetonitrile at 35℃; for 20h; Reagent/catalyst; Chan-Lam Coupling; Irradiation;	100%
With 2,6-dimethylpyridine; tetrabutylammonium perchlorate; copper diacetate; triethylamine In acetonitrile at 20℃; for 20h; Chan-Lam Coupling; Electrochemical reaction; chemoselective reaction;	45%
With copper(II) acetate monohydrate Chan-Lam Coupling;
With C32H32Cl2Cu2N4O4; triethylamine In ethanol for 5h;	93 %Chromat.

5-ethyl-3-iodo-2,5-dihydrofuran-2-one (1206522-04-4) + 4-Chlorophenylboronic acid (1679-18-1) → 3-(4-chlorophenyl)-5-ethylfuran-2(5H)-one

Conditions	Yield
With 1,1',1'',1'''-benzene-1,2,4,5-tetrayltetrakis(methylene)tetrakis-(piperidin-4-ol); palladium diacetate; potassium carbonate In ethanol; water at 20℃; for 0.25h; Suzuki-Miyaura Coupling;	100%

4-Chlorophenylboronic acid (1679-18-1) + p-toluidine (106-49-0) → (4-chlorophenyl)(4-methylphenyl)amine (21648-16-8)

Conditions	Yield
With 2,6-dimethylpyridine; fac-tris(2-phenylpyridinato-N,C2')iridium(III); copper diacetate; n-tetradecanoic acid In toluene; acetonitrile at 35℃; for 20h; Reagent/catalyst; Chan-Lam Coupling; Irradiation;	100%
With 2,6-dimethylpyridine; tetrabutylammonium perchlorate; copper diacetate; triethylamine In acetonitrile at 20℃; for 20h; Chan-Lam Coupling; Electrochemical reaction; chemoselective reaction;	97%
With C32H32Cl2Cu2N4O4; triethylamine In ethanol for 5h;	94 %Chromat.

4-Chlorophenylboronic acid (1679-18-1) + o-toluidine (95-53-4) → N-(4-chlorophenyl)-2-methylaniline (113965-93-8)

Conditions	Yield
With 2,6-dimethylpyridine; fac-tris(2-phenylpyridinato-N,C2')iridium(III); copper diacetate; n-tetradecanoic acid In toluene; acetonitrile at 35℃; for 20h; Reagent/catalyst; Chan-Lam Coupling; Irradiation;	100%
With 2,6-dimethylpyridine; tetrabutylammonium perchlorate; copper diacetate; triethylamine In acetonitrile at 20℃; for 20h; Chan-Lam Coupling; Electrochemical reaction; chemoselective reaction;	84%
With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper; acetic acid In acetonitrile	47%

4-Chlorophenylboronic acid (1679-18-1) + 4-bromopyridine hydrobromide salt → 4-(4-chlorophenyl)pyridine (5957-96-0)

Conditions	Yield
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium carbonate In 1,4-dioxane; water at 110℃; for 16h; Inert atmosphere;	100%

N-acetyl-2-bromoaniline (614-76-6) + 4-Chlorophenylboronic acid (1679-18-1) → N-[4’-chloro-(1,1’-biphenyl)-2-yl]acetamide

Conditions	Yield
With potassium phosphate tribasic heptahydrate; 10 wt% Pd(OH)2 on carbon; tetrabutylammomium bromide In N,N-dimethyl-formamide at 125℃; for 11h; Reagent/catalyst; Solvent; Temperature; Time; Suzuki Coupling;	100%
With di-tert-butyl(phenyl)phosphonium tetrafluoroborate; bis(acetylacetonato)palladium(II) In water; butan-1-ol at 60℃; for 20h; Reagent/catalyst; Suzuki Coupling; Inert atmosphere;
With di-tert-butyl(phenyl)phosphonium tetrafluoroborate; palladium(II) acetylacetonate In aq. phosphate buffer; butan-1-ol at 60℃; for 13h; pH=7 - 10; Reagent/catalyst; Suzuki Coupling; Inert atmosphere;

1-(4-bromobenzyl)-1H-indole-3-carboxylic acid methyl ester (709004-41-1) + 4-Chlorophenylboronic acid (1679-18-1) → 1-((4'-chloro-[1,1'-biphenyl]-4-yl)methyl)-1H-indole-3-carboxylic acid methyl ester

Conditions	Yield
With palladium diacetate; sodium carbonate; triphenylphosphine In dimethyl sulfoxide at 80℃; Suzuki Coupling; Inert atmosphere;	100%
With palladium diacetate; sodium carbonate; triphenylphosphine In dimethyl sulfoxide at 80℃; Inert atmosphere;	93%

2-bromo-2’-fluoro-1,1’-biphenyl (1554-05-8) + 4-Chlorophenylboronic acid (1679-18-1) → 4''-chloro-2-fluoro-1,1':2',1''-terphenyl

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In N,N-dimethyl acetamide; water at 80℃; for 18h; Suzuki Coupling; Inert atmosphere;	100%

4-Chlorophenylboronic acid (1679-18-1) + Cinnamyl bromide (4392-24-9) → (E)-1-chloro-4-(3-phenyl-2-propen-1-yl)benzene (6948-68-1)

Conditions	Yield
With potassium carbonate; (3E,8E,13E)-1,6,11-[(2,4,6-iPr3Ph)SO2]3-1,6,11-C15H18N3Pd(0) In toluene at 80℃; for 4h; Arylation;	99%
With dihydrogen peroxide; potassium carbonate; Pd(dba)n (n = 1.5-2) 1.) benzene, reflux, 15 h, 2.) r.t., 1 h; Multistep reaction;

4-Chlorophenylboronic acid (1679-18-1) → 4,4'-dichlorobiphenyl (2050-68-2)

Conditions	Yield
With (N-piperazinyl-N′-methyl)-2-methylene-4,6-di-tert-butylphenol; palladium diacetate; potassium carbonate In ethanol at 20℃; for 12h; Solvent; Reagent/catalyst; Time; Concentration; Suzuki Coupling; Green chemistry;	99%
With sodium hydroxide In water at 120 - 130℃; Microwave irradiation;	99%
With potassium acetate; silver(l) oxide In methanol at 40℃; for 15h;	99%

Upstream product

• 89566-59-6 di-(p-chlorophenyl)borinic acid 
• 873-77-8 (4-chlorphenyl)magnesium bromide 
• 637-87-6 1-Chloro-4-iodobenzene 
• 106-39-8 bromochlorobenzene 
• 7519-91-7 tris(4-chlorophenyl)boroxine 
• 5419-55-6 Triisopropyl borate 
• 13283-31-3 borane 
• 7637-07-2 boron trifluoride 
• 15799-48-1 tetra(p-chlorophenyl)tin 
• 141-43-5 ethanolamine 
• 121-43-7 Trimethyl borate 
• 120208-73-3 1,2-bis(p-chlorophenyl)diborane⁽⁶⁾ 
• 7732-18-5 water 
• 95890-68-9 2-(4-chlorophenyloxy)-2-(4-chlorophenyl)-5-methyl-3,3-tetramethylen-1-oxa-3-azonia-2-boratacyclopentane 

Downstream Products

• 113977-51-8 diethyl 4-chlorophenylboronate 
• 7519-91-7 tris(4-chlorophenyl)boroxine 
• 36165-58-9 5-bromo-2-(4-chloro-phenyl)-5-nitro-[1,3,2]dioxaborinane 
• 36165-59-0 5-chloro-2-(4-chloro-phenyl)-5-nitro-[1,3,2]dioxaborinane 
• 36165-57-8 2-(4-chloro-phenyl)-5,5-dinitro-[1,3,2]dioxaborinane 
• 36165-56-7 5-chloromethyl-2-(4-chloro-phenyl)-5-nitro-[1,3,2]dioxaborinane 
• 65748-15-4 3-benzyl-2-(4-chloro-phenyl)-5-methyl-5-nitro-[1,3,2]oxazaborinane 
• 65748-17-6 3-tert-butyl-2-(4-chloro-phenyl)-5-methyl-5-nitro-[1,3,2]oxazaborinane 
• 24341-83-1 2-(4-chlorophenyl)-2,3-dihydrobenzo[d][1,3,2]diazaborinin-4(1H)-one 
• 109097-22-5 methyl O⁴,O⁶-(4-chloro-phenylboranediyl)-α-D-glucopyranoside 
• 24067-16-1 2-(4-chloro-phenyl)-1-phenyl-2,3-dihydro-1H-benzo[1,3,2]diazaborole 
• 138647-50-4 4-(4-Chloro-phenyl)-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester 
• 158959-34-3 1-[2-(4-chlorophenyl)cyclopenten-1-yl]-4-(methylsulfonyl)benzene 
• 6948-68-1 (E)-1-chloro-4-(3-phenyl-2-propen-1-yl)benzene 

Relevant academic research and scientific papers

SYNTHESIS OF ARYLBORONIC ACIDS VIA THE REACTION OF BORANE WITH ARYLMAGNESIUM HALIDES

The reaction of borane complexes with arylmagnesium halides produces the corresponding arylborohydrides in high yield.The arylborohydrides are readily hydrolyzed to the arylboronic acids.The syntheses are conveniently carried out in one pot.The reaction mechanism was clarified via a boron-11 NMR study.

Preparation method of monohalogenated phenylboronic acid

The invention relates to the technical field of chemical synthesis, and particularly discloses a preparation method of monohalogenated phenylboronic acid. The preparation method comprises the following steps of: by taking dihalogenated benzene as a raw material and a mixture of lithium salt and alkaline ionic liquid as a catalyst, carrying out Grignard exchange with R1MgCl to generate monohalogenated phenyl magnesium chloride, reacting with B (OR) 3 to generate monohalogenated phenyl borate, and hydrolyzing under acidic conditions to obtain monohalogenated phenylboronic acid. The HPLC (High Performance Liquid Chromatography) content of the monohalogenated phenylboronic acid prepared by the method is greater than 99.5%; the total yield of the product is greater than 80%, the contents of monohalogenated phenylboronic acid and phenyldiboronic acid impurities of another halogen are both less than 0.003%, the requirements of modern fine chemical synthesis are completely met, the raw materials are easily available, the operation is simple, the safety is high, and the industrial production of monohalogenated phenylboronic acid is realized.

Pd- And Ni-Based Systems for the Catalytic Borylation of Aryl (Pseudo)halides with B2(OH)4

Despite recent advancements in metal-catalyzed borylations of aryl (pseudo)halides, there is a continuing need to develop robust methods to access both early-stage and late-stage organoboron intermediates amendable for further functionalization. In particular, the development of general catalytic systems that operate under mild reaction conditions across a broad range of electrophilic partners remains elusive. Herein, we report the development and application of three catalytic systems (two Pd-based and one Ni-based) for the direct borylation of aryl (pseudo)halides using tetrahydroxydiboron (B2(OH)4). For the Pd-based catalyst systems, we have identified general reaction conditions that allow for the sequestration of halide ions through simple precipitation that results in catalyst loadings as low as 0.01 mol % (100 ppm) and reaction temperatures as low as room temperature. We also describe a complementary Ni-based catalyst system that employs simple unligated Ni(II) salts as an inexpensive alternative to the Pd-based systems for the borylation of aryl (pseudo)halides. Extrapolation of all three systems to a one-pot tandem borylation/Suzuki-Miyaura cross-coupling is also demonstrated on advanced intermediates and drug substances.

Aryl boronic acid preparation method

The invention belongs to the technical field of fine chemical engineering, and relates to an aryl boronic acid preparation method. In the prior art, aryl boronic acid as a novel safe and environmentally-friendly arylation reagent is widely used in scientific research and production of various fine chemicals containing aryl structures in the fields of medicines, pesticides, advanced materials and the like; and the aryl boronic acid compound preparation method reported in the disclosed literature has problems of harsh reaction conditions and high cost. A purpose of the invention is to provide amethod, wherein an aryl boron compound is formed by carrying out a reaction on a Grignard reagent and trialkyl borate under mild conditions, the composition of the aryl boron compound is converted from the main component diaryl borate into the main component aryl borate, and the aryl borate is hydrolyzed to obtain aryl boric acid, so that the preparation cost of the acyl aryl boric acid compound can be remarkably reduced, and the method has good practical application prospect.

Synthesis method of P-chlorophenylboronic acid

The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of p-chlorophenylboronic acid, which comprises the following steps: carrying out Friedel-Crafts reaction between chlorobenzene used as a raw material and boron trichloride under the action of a catalyst to obtain dichloro(4-chlorophenyl) borane, and carrying out acidic hydrolysis to obtain p-chlorophenylboronic acid. According to the method, p-chlorophenylboronic acid is synthesized by taking chlorobenzene as a raw material through a Friedel-Crafts reaction, and the method has theadvantages of novel synthesis route, simple and practical operation, easily available raw materials, low cost, environmental friendliness, and the like.

Magnesium promoted autocatalytic dehydrogenation of amine borane complexes: A reliable, non-cryogenic, scalable access to boronic acids

Owing to the unusual reactivity of dialkylamine-borane complexes, a methodology was developed to simply access boronic acids. The intrinsic instability of magnesium aminoborohydride was tweaked into a tandem dehydrogenation borylation sequence. Proceeding via an autocatalytic cycle, amineborane dehydrogenation was induced by a variety of Grignard reagents. Overall, addition of the organomagnesium species onto specially designed dialkylamine-borane complexes led to a variety of boronic acids in high yields. In addition, the reaction can be performed under Barbier conditions, on a large scale.

Preparation method of 4-chlorophenylboronic acid

The invention belongs to the technical field of organic synthesis and particularly relates to a preparation method of 4-chlorophenylboronic acid. The preparation method has the advantages that reaction conditions are optimized, the used raw materials are economical, low raw material cost is achieved, the mixed solvent of toluene and tetrahydrofuran is used to replace a single tetrahydrofuran solvent, p-dichlorobenzene replaces p-chlorobromobenzene to serve as the main raw material of Grignard reaction, discharge in water is achieved through condensation reaction with trimethyl borate or tributyl borate and post-treatment, raw material and solvent costs are saved greatly, yield is increased, and the preparation method is high in yield, low in cost, evident in competitive advantage and convenient to achieve industrial production.

Copper-Catalyzed Monoorganylation of Trialkyl Borates with Functionalized Organozinc Pivalates

Organozinc pivalates, a recently developed air- and moisture-stable organozinc species, were found for the first time as excellent organometallic species in the monoorganylation of trialkyl borates whereby boronic acids were prepared in high yields. The significant advantage of organozinc pivalates over another previously employed organometallic reagents, e. g., organolithium reagents, Grignard reagents and organozinc halides, is that the generation of multiorganylation byproducts such as borinic acids and trialkylboranes were completely suppressed. Additionally, the in situ generated boronates could be directly arranged into Suzuki-Miyaura type cross-coupling reactions to produce biaryls in high yields.

Method for preparing chlorophenylboronic acid

The invention discloses a method for preparing chlorophenylboronic acid. The method has the advantages that existing Grignard reagent processes are improved, Grignard reaction and substitution reaction are combined with each other and are carried out at a step, accordingly, ultralow-temperature control can be omitted, energy consumption can be obviously reduced, the operation difficulty can be obviously lowered, byproducts can be reduced, and the yield of target products can be increased.

Bedford-type palladacycle-catalyzed miyaura borylation of aryl halides with tetrahydroxydiboron in water

A mild aqueous protocol for palladium catalyzed Miyaura borylation of aryl iodides, aryl bromides and aryl chlorides with tetrahydroxydiboron (BBA) as a borylating agent is developed. The developed methodology requires low catalyst loading of Bedford-type palladacycle catalyst (0.05 mol %) and works best under mild reaction conditions at 40 °C in short time of 6 h in water. In addition, our studies show that for Miyaura borylation using BBA in aqueous condition, maintaining a neutral reaction pH is very important for reproducibility and higher yields of corresponding borylated products. Moreover, our protocol is applicable for a broad range of aryl halides, corresponding borylated products are obtained in excellent yields up to 93% with 29 examples demonstrating its broad utility and functional group tolerance.