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CAS No. : | 4612-26-4 | MDL No. : | MFCD00236018 |
Formula : | C6H8B2O4 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | BODYVHJTUHHINQ-UHFFFAOYSA-N |
M.W : | 165.75 | Pubchem ID : | 230478 |
Synonyms : |
|
Num. heavy atoms : | 12 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 2 |
Num. H-bond acceptors : | 4.0 |
Num. H-bond donors : | 4.0 |
Molar Refractivity : | 46.09 |
TPSA : | 80.92 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | Yes |
Log Kp (skin permeation) : | -7.5 cm/s |
Log Po/w (iLOGP) : | 0.0 |
Log Po/w (XLOGP3) : | -0.27 |
Log Po/w (WLOGP) : | -2.95 |
Log Po/w (MLOGP) : | -1.47 |
Log Po/w (SILICOS-IT) : | -3.26 |
Consensus Log Po/w : | -1.59 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -0.94 |
Solubility : | 19.2 mg/ml ; 0.116 mol/l |
Class : | Very soluble |
Log S (Ali) : | -0.97 |
Solubility : | 17.7 mg/ml ; 0.107 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -0.17 |
Solubility : | 112.0 mg/ml ; 0.675 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.96 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P264-P270-P301+P312-P501 | UN#: | N/A |
Hazard Statements: | H302 | Packing Group: | N/A |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.6% | Stage #1: With iodine; magnesium In tetrahydrofuran at 30℃; for 3 h; Inert atmosphere Stage #2: at -70℃; for 1 h; |
under the protection of nitrogen, into 200 ml THF, 15 . 0g (0.62 µM) magnesium,1.0g(0.004mol)I2, slowly dropping containing 68.4g (0.29 µM) of the two 1, 4 - bromobenzene 300 ml THF solution, adds by drops in 30 °C reaction 3h, cooling to -70 °C, slowly dropping boric acid three methyl ester (78.5 ml, 0 . 72 µM) and 300 ml THF of a mixed solution of the, completion of the dropping, for -70 °C reaction 1h, Slowly to room temperature stirring 12h. Adding 2.5M HCl950ml fast stirring 15min, filtering, with 300 ml hexane washing three times, vacuum drying, the white solid obtained 40.7g, yield of 84.6percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With C37H45ClN2O3PPd; potassium carbonate In ethanol; water at 80℃; for 6 h; Inert atmosphere; Schlenk technique | A 10-mL round-bottom flask was charged with the prescribe damount of catalyst, 1,4-benzenediboronic acid (0.5 mmol), N-heteroaryl halides (1.5 mmol), the selected base (1.5 mmol) and solvent (4 mL). The flask was placed in an oil bath and heated at 80 °C for 6 h, then cooled to room temperature and extracted with CH2Cl2. The crude products obtained from evaporation were purified by flash chromatography on silica gel. The products 5b–c, 5f, 5m [21], 5d [22], 5e [23], 5l [24] were known compounds and characterized by the comparison of data with those in the literature. The products 5a, 5g–k, 5n–o were new compounds and characterized by elemental analysis, IR, MS,1H and 13C NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 2 h; | 2-bromo-naphthalene (2.07g, 10mmol), benzene-1,4-diBoronic acid(2.49g, 15mmol), Pd (PPh3) 4 (0.58 g, 0.5mmol), potassium carbonate (4.15g, 30mmol) and THF: H2O = 2:1 solution dissolved in 200ml 80 After 2 hours reflux agitation. Thereafter it was added and extracted three times with 40ml ethyl ether H2O40ml drying the obtained organic layer with magnesium sulfate, and separating the residue obtained by evaporating the solvent was subjected to silica gel column chromatography purification Intermediate B-1 (1.98g, 80percent yield) It was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
9.8 g | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene for 6 h; Inert atmosphere; Reflux | Will 10 grams of 4-bromopyridine,11 grams of 1,4-benzenediboronic acid,20 grams of sodium carbonate,120 ml of toluene,80 ml of ethanol,40 ml of water was added to a 500 ml three-necked bottle.Under nitrogen protection,0.65g of Pd(pph3)4 was added,Heated to reflux,The reaction is complete after 6 hoursCooling,The solid obtained by suction filtrationWash with ethyl acetate,Get the product,9.8 grams. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | In DMF (N,N-dimethyl-formamide); at 20℃; for 12h; | Following a standard procedure (Nicolas, M. et al., Eur. [J ; ORG CHEM.] 2000,1703- 1710; [ISHIYAMA,] T. et [AL.,] Tetrahedron Lett. 1997, [38,] 3447-3450; Yu, L. and Lindsey, J. S. Tetrahedron 2001, 57, 9285-9298) for forming dioxaborolanes but with use of DMF instead of ether to achieve solubility of the bis (boronic acid), samples of [1,] 4-bis (dihydroxyboryl) benzene (5.158 g, 31.1 mmol) and pinacol (8.83 g, 74.7 mmol) were dissolved in anhydrous DMF (100 mL). The reaction mixture was stirred for 12 h at room temperature, affording a white solid. Water (100 mL) was added and the reaction mixture was filtered. The resulting white solid was dried (9.23 g, 93%). Physical data for this compound are identical to the literature (Shultz, D. A. et [AL., J : ORG CHEM.] 1999, 64, [9124-9136).] |
62% | With magnesium sulfate; In methanol; at 30℃; for 24h; | A mixture of 1,4-phenylenediboronic acid (8.3 mmol, 1.37 g), pinacol (20.65 mmol, 2.44 g) methanol (20 mL) and SO4Mg (22.0 mmol,2.65 g), was heated at 30 C for 24 h. After this period, methanol was evaporated. The resulting solid was dissolved in CHCl3 (50 mL), dried with SO4Mg and the solvent was removed under reduced pressure. The product was washed with toluene/hexane (2:1) to give white crystals. Yield: 1.71 g(62%), mp 239 C. NMR characterizations were consistent with thosepreviously reported in ref. 40. 1H RMN (CDCl3): delta=7.79 (s, 1 H), 1.34 (s,6 H). 13C RMN (CDCl3): delta=134.3, 84.2, 25.3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With C37H28N8O*2Cl(1-)*Pd(2+); potassium carbonate; In ethanol; at 70℃; for 2h; | General procedure: Arylhalide (5.0 mmol) and phenylboronic acid (5.0 mmol), K2CO3 (5.0 mmol) and X-Pd3L (0.005 mol% Pd loading) were added to a solutionof 12 mL EtOH under ambient atmosphere. The mixture was stirred at 70 C for 2 h. After cooling, H2O (10 mL) was added into the resultant mixture and the product was extracted by ethyl acetate (3 × 10 mL). The organic phase was combined and dried over Na2SO4. After removal of solvent, the product was dried at 60 C. In most cases, the products are pure (analyzed by 1H NMR spectroscopy) because it is an equal stoichiometric reaction and the substrates are completely converted into product. If the product is impure, the purification can be performed ona silica gel chromatography (hexane:ether = 60:1 as an eluent). All products were confirmed by 1H and 13C NMR and compared with literatures (see SI). For the recycled experiment, the xerogel catalyst was recovered by centrifugation and washed with EtOH (3 × 4 mL) after reaction, then dried in air. |
86% | With palladium; potassium carbonate; In methanol; acetonitrile; at 20℃; for 2h; | General procedure: To a freshly prepared solution of PdNPs (10 mL, 0.02 mmol), required amount of K2CO3 (2 mmol) was added followed by aryldihalides/ arylhalide (1 mmol) and arylboronic acid (3 mmol)/diboronic acid (0.75 mmol). Then, the reaction mixture was stirred at room temperature in open atmosphere. The reaction was monitored by TLC and was stopped after the complete consumption of starting material. The desired product got precipitated out which was separated by filtration and extracted with chloroform. The chloroform layer was evaporated to get the terphenyl in pure state. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; for 24h;Heating / reflux; | Under N atmosphere, compound B (11.06 g, 30.08 mmol), phenyl- 1,4-diboronic acid (1.6 g, 15.04 mmol), and Pd(PPh ) (0.52 g, 0.45 mmol) were added to an aqueous3 42 M K CO solution (50 mL) and THF (150 mL). The mixture was refluxed under stirring for about 24 hours. After completing the reaction, the mixture was cooled to room temperature. The organic layer was separated from the reaction mixture, and filtered to obtain a solid. This solid was recrystallized from THF and ethanol to obtain a compound E (9.04 g, 92percent). [69] MS [M] = 650 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
6.94 g (21.7 mmol) of 2-iodo-9,9- dimethylfluorene and 1 g (7.25 mmol) of 1,4- phenylenebis (boronic acid) were dissolved and agitated under nitrogen flow in the mixed solvent (120 ml of degassed toluene and 60 ml of ethanol), and 145 ml of sodium carbonate solution which was prepared by dissolving 30 g of anhydrous sodium carbonate in 150 ml of water was added dropwise thereto. After agitating for 30 minutes, 840 mg (0.727 mmol) of tetrakis (triphenylphosphine) palladium was added. Heating with agitation was carried out on the oil bath heated at [80°C] for about 3 hours. After cooling the reaction solution to room temperature, 50 ml of water and 50 ml of ethyl acetate were added, the aqueous layer and the organic layer were separated, the aqueous layer was further extracted with toluene and ethyl acetate, and the extract combined with the above organic layer was dried over magnesium sulfate. The solvent was evaporated, the residual substance was refined by silica gel column chromatography (toluene: hexane = 1: 2), and 3.02 g of 1, 4-phenylenebis (9,9- dimethylfluorene) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50%; 7% | With sodium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,2-dimethoxyethane; water; at 90℃; for 0.5h; | Example E-16; 3- 4-Boronic acid-phenvl)-4-cyano-5-ethvl-thiophene-2-carboxvlic acid ethyl ester; Stir and heat the mixture of 4-cyano-5-ethyl-3-iodo-thiophene-2-carboxylic acid ethyl ester (500 mg, 1.49 mmol), bis-phenylboronic acid (500 mg, 3 mmol, 2 eq), 1,1'- bis (diphenylphosphino) ferrocenedichloropalladium (II) (130 mg, 0.149 mmol, 0.1 eq) in sodium carbonate 2M solution (3 ml, 5.96 mmol, 4 eq) and DME (12.5 ml) at 90°C for 30 min. Pour the reaction mixture into water and extract with dichloromethane. Wash the dichloromethane extract with HC110percent and dry (MgS04). Filter the MgS04 and concentrate the filtrate under reduced pressure to afford a light brown powder. Purification by extraction cartridge (waters Oasis HLB 20cc, 1 gr LP Extraction cartridges) to provide the title compound in 50percent yield: Mass spectrum (EI+) : m/z 330 (M++1) ; 1H NMR (CDC13, 200 MHz): 88. 0 (s abr. 2H) ; 7.78 (d, 2H, J= 8. 06) ; 7.4 (d, 2H, J= 8.06) ; 4.18 (q, 2H, J=7. 2) ; 3.08 (q, 2H, J=7.2) ; 1.43 (t, 3H, J=7. 5) ; 1.17 (t, 3H, J=7. 2) plus biscoupled product 4-Cyano-5-ethyl-3-{4-(4-cyano-5-ethyl) thiophen-3-yl-phenyl}- thiophene-2-carboxylic acid ethyl ester in 7percent yield Mass spectrum (EI+) : m/z 493. (M++1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 100℃; for 5h; | A solution containing 2 (3.3 g, 8.3 mmol) in toluene (25 mL), EtOH (25 mL), and water (1 mL) was degassed under high vacuum. K2CO3 (4.5 g, 32.5 mmol), 3 (0.97 g, 5.8 mmol), and (Ph3P)4Pd (0.29 g, 0.25 mmol) were added and the resulting mixture was stirred at 100° C. for 5 h. [TLC analysis, 4:1 hexane/EtOAc, Rf(2)=0.5; Rf(4)=0.3]. The reaction mixture was filtered through a short pad of silica gel and washed with 5percent EtOAc/hexane. The filtrate was concentrated and the crude product was purified by flash silica gel chromatography (20percent EtOAc/hexane) to afford 3.0 g (98percent) of 4 as an off-white, highly-fluorescent solid. 1H NMR (CDCl3, 300 MHz) delta8.6-8.4 (m, 2H), 7.65 (m, 2H), 7.57 (br s, 4H), 7.05 (m, 2H), 7.90 (m, 2H), 4.22 (br s, 2H), 3.4-3.1 (m, 6H), 2.90 (m, 2H), 1.8-1.3 (m, 26H) ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In methanol; water; toluene; at 80℃; for 12h; | Example 3; 5-[4-(5-Formylfuran-2-yl)-phenyl]-furan-2-carboxaldehyde (11); To a stirred solution of 5-bromofuran-2-carboxaldehyde (10 mmol), and tetrakis(triphenylphosphine) palladium (400 mg) in toluene (20 mL) under a nitrogen atmosphere was added 10 mL of a 2 M aqueous solution of Na2CO3 followed by 1,4-phenylenebisboronic acid (5 mmol) in 6 mL of methanol. The vigorously stirred mixture was warmed to 80 °C for 12 h. The solvent was evaporated, the precipitate was partitioned between methylene chloride (300 mL) and 2 M aqueous Na2CO3 (15 mL) containing 5 mL of concentrated ammonia. The organic layer was dried (Na2SO4), and then concentrated to dryness under reduced pressure to afford 11 in 93percent yield; mp 233-234 °C (EtOH). 1H NMR (DMSO-d6); delta 9.64 (s, 2H), 8.01 (s, 4H), 7.70 (d, J = 3.6 Hz, 2H), 7.43 (d, J = 3.6 Hz, 2H). MS (ESI) m/e (rel. int.): 266 (M+, 100), 238 (5), 209 (25). Anal. Calc. for C16H10O4: Cpercent 72.16; Hpercent 3.78; Found Cpercent 72.41; Hpercent 3.93. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With potassium phosphate;palladium diacetate; tri-tert-butyl phosphine; In xylene; at 140℃; for 3h; | 31.37 g of intermediate (1-d), 5 g of phenyl-1,4-diboronic acid, 14.49 g of tripotassium phosphate, 27 mg of palladium acetate, 49 mg of tris(tert-butyl)phosphine and 60 mL of xylene were mixed in a reaction vessel and heated to 140° C. under a nitrogen blanket. The reaction mixture was stirred for 3 hours, and then 240 mL of toluene was added. The mixture was filtered while hot at 100° C. Next, the filtrate was concentrated by evaporation, and the residue was dried to yield a yellow solid. The solid was purified by sublimation to yield 14.1 g (yield 59percent) of compound H10. Tg=202° C. and Tm=427° C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With palladium; potassium carbonate; In methanol; acetonitrile; at 20℃; for 2h; | General procedure: To a freshly prepared solution of PdNPs (10 mL, 0.02 mmol), required amount of K2CO3 (2 mmol) was added followed by aryldihalides/ arylhalide (1 mmol) and arylboronic acid (3 mmol)/diboronic acid (0.75 mmol). Then, the reaction mixture was stirred at room temperature in open atmosphere. The reaction was monitored by TLC and was stopped after the complete consumption of starting material. The desired product got precipitated out which was separated by filtration and extracted with chloroform. The chloroform layer was evaporated to get the terphenyl in pure state. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; for 3h;Heating / reflux; | 1.5 g of 5-(6-bromopyridin-2-yl)-5H-pyrido[4,3-b]indol, 0.4 g of benzene-1,4-diboronic acid, 11 ml of a 2M potassium carbonate aqueous solution, 74 mg of tetrakis(triphenylphosphine)palladium(0), 120 ml of toluene, and 30 ml of ethanol were added and the whole was stirred for 3 hours under heating and reflexing. After cooling to room temperature, insoluble solid was removed by filtration. The resulting solid was dissolved in a mixed solution of chloroform/methanol and insoluble solid was removed by filtration. Thereafter, the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by recrystallization from methanol to obtain 0.91 g (yield 76percent) of 1,4-bis[5H-pyrido[4,3-b]indol-5-yl-pyridine-6-yl]benzene (Compound 129) as a yellow white powder. The structure of the resulting yellow white powder was identified using NMR. The results of 1H-NMR measurement are shown in FIG. 8. The following 24 hydrogen signals were detected on 1H-NMR (CDCl3-CD30D) delta (ppm) = 9.35 (2H), 8.54 (2H), 8.31 (4H), 8.23 (2H), 8.11 (2H), 7.93-98 (4H), 7.87 (2H), 7.54-64 (4H), 7.45 (2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With C37H28N8O*2Cl(1-)*Pd(2+); potassium carbonate; In ethanol; at 70℃; for 2h; | General procedure: Arylhalide (5.0 mmol) and phenylboronic acid (5.0 mmol), K2CO3 (5.0 mmol) and X-Pd3L (0.005 molpercent Pd loading) were added to a solutionof 12 mL EtOH under ambient atmosphere. The mixture was stirred at 70 °C for 2 h. After cooling, H2O (10 mL) was added into the resultant mixture and the product was extracted by ethyl acetate (3 × 10 mL). The organic phase was combined and dried over Na2SO4. After removal of solvent, the product was dried at 60 °C. In most cases, the products are pure (analyzed by 1H NMR spectroscopy) because it is an equal stoichiometric reaction and the substrates are completely converted into product. If the product is impure, the purification can be performed ona silica gel chromatography (hexane:ether = 60:1 as an eluent). All products were confirmed by 1H and 13C NMR and compared with literatures (see SI). For the recycled experiment, the xerogel catalyst was recovered by centrifugation and washed with EtOH (3 × 4 mL) after reaction, then dried in air. |
94% | With 1,3-bis[3-(3-phenylpropyl)-1-ylbenzimidazolium]propane dibromide; palladium diacetate; potassium carbonate; In water; N,N-dimethyl-formamide; at 100℃; for 0.0833333h;Microwave irradiation; | General procedure: Bromobenzene (1 mmol) or 1-bromonaphthalene (1 mmol), phenylboronic acid (1 mmol), or benzene-1,4-diboronic acid (0,5 mmol), K2CO3 (2 mmol), Pd(OAc)2 (1 molpercent), 1a?1h (2 molpercent), and DMF (3 mL)-H2O(3 mL) were added to an apparatus of microwave equipment. The mixture was stirred and heated at 100 °C by microwave irradiation (300 W) for 5 min. After the completion of the reaction, the product was extracted with ethyl acetate from the mixture. Then the purification was done by crystallization from ethyl acetate/n-hexane(1:1). The isolated yield was calculated. The product structures were determined by 1 H-NMR, 13 C-NMR, and LC-MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water;Reflux; Inert atmosphere; | 6) (5-{4-[5-(4-Methyl-piperazine-1-carbonyl)-furan-2-yl]-phenyl}-furan-2-yl)-(4-methyl-piperazin-1-yl)- methanone (r237) [Show Image] Palladium tetrakistryphenilphosphine (40 mg, 36 mumol) was added to a stirred solution of (5-Bromo-furan-2-yl)-(4-methyl-piperazin-1-yl)-methanone (0.40 g, 1.4 mmol) and 1,4-phenylene diboronic acid (0.12 g, 0.7 mmol) in degassed dioxane (15 mL) and saturated aqueous sodium carbonate (8 mL). The reaction mixture was refluxed overnight under Argon atmosphere. After evaporation of the solvent, the crude was purified by flash chromatography (89:10:1 CHCl3: EtOH: Et3N,) giving 260 mg (80percent) of (5-{4-[5-(4-Methyl-piperazine-1-carbonyl)-furan-2-yl]-phenyl}-furan-2-yl)-(4-methyl-piperazin-1-yl)- methanone. 1H NMR (CDCl3, 400 MHz), delta (ppm): 7.70 (s, 4H), 7.26 (d, 2H, J =3.6 Hz), 6.78 (d, 2H, J =3.6 Hz), 3.94 (bs, 8H), 2.40 (s, 6H), 1.85 (bs, 8H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With potassium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,2-dimethoxyethane; water; at 100℃; for 2h; | 1 ,1 -dimethylethyl(2S)-2-(5-bromo-1 H-benzimidazol-2-yl)-1 -pyrrolidinecarboxylate (intermediate 45a) (5.00g, 12.76 mmol), benzene-1 ,4-diyldiboronic acid 3 (1 .057 g, 6.38 mmol), PdCI2(dppf)-CH2CI2 adduct (0.512 g, 0.638 mmol), potassium carbonate (2.76 g, 20 mmol) in 1 ,2-dimethoxyethane (30 mL) and water (10 mL) were heated in an oil bath at 100°C for 2 hours. The sample was filtered through celite and washed with DCM. The sample was concentrated and the residue partitioned between DCM and water, the organic layer dried with MgSO^ filtered and concentrated. The residue was chromatographed on a silica using 0-5percent (2N NH3 in MeOH) in DCM. Fractions were concentrated to yield bis(1, 1- dimethylethyl) (2S,2'S)-2,2'-[benzene-1 -diylbis(1H-benzimidazole-5,2-diyl)]di pyrrolidinecarboxylate) (2.50 g, yield 55percent) as an orange solid. 1H NMR (400 MHz, DMSO-c/e) delta ppm 12.03 (br. s., 2 H) 7.83 - 7.89 (m, 1 H) 7.75 (s, 5 H) 7.61 (s, 1 H) 7.52 (br. s., 3 H) 4.99 (br. s., 2 H) 3.79 (td, J=3.4, 1 .6 Hz, 1 H) 3.61 (br. s., 2 H) 3.48 (dt, J=10.2, 7.1 Hz, 2 H) 3.20 (d, J=5.3 Hz, 2 H) 2.34 (br. s., 2 H) 2.05 (d, J=5.9 Hz, 4 H) 1 .93 (d, J=7.1 Hz, 2 H) 1 .28 (br. s., 18 H). ES LC-MS m/z =672.2 (M+H).Intermediate 5 |
23% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene;Reflux; Inert atmosphere; | Step Ic. A mixture of the compound from step Ib (0.500 g, 1.37 mmol), benzene-1,4- diboronic acid (0.103 g, 0.621 mmol) and Pd(PPh3)4 (35.8 mg, 31.0 mumol) in ethanol (6 mL), toluene (6 mL) and aqueous Na2CO3 (2 M, 0.4 mL) was degassed and heated to reflux under N2 overnight. The volatiles were evaporated and the residue was partitioned (EtOAc - saturated aqueous NaHCO3). The organics were washed with brine, dried (Na2SO4), filtered and evaporated. The residue was purified by flash column chromatography (silica, hexanes-ethyl acetate) to give the title compound as a yellow solid (0.158 g, 23percent). ESIMS m/z = 649.50 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With C37H45ClN2O3PPd; potassium carbonate; In ethanol; water; at 80℃; for 6h;Inert atmosphere; Schlenk technique; | A 10-mL round-bottom flask was charged with the prescribe damount of catalyst, 1,4-benzenediboronic acid (0.5 mmol), N-heteroaryl halides (1.5 mmol), the selected base (1.5 mmol) and solvent (4 mL). The flask was placed in an oil bath and heated at 80 °C for 6 h, then cooled to room temperature and extracted with CH2Cl2. The crude products obtained from evaporation were purified by flash chromatography on silica gel. The products 5b?c, 5f, 5m [21], 5d [22], 5e [23], 5l [24] were known compounds and characterized by the comparison of data with those in the literature. The products 5a, 5g?k, 5n?o were new compounds and characterized by elemental analysis, IR, MS,1H and 13C NMR. |
62% | With palladium; potassium carbonate; In methanol; acetonitrile; at 20℃; for 2.5h; | General procedure: To a freshly prepared solution of PdNPs (10 mL, 0.02 mmol), required amount of K2CO3 (2 mmol) was added followed by aryldihalides/ arylhalide (1 mmol) and arylboronic acid (3 mmol)/diboronic acid (0.75 mmol). Then, the reaction mixture was stirred at room temperature in open atmosphere. The reaction was monitored by TLC and was stopped after the complete consumption of starting material. The desired product got precipitated out which was separated by filtration and extracted with chloroform. The chloroform layer was evaporated to get the terphenyl in pure state. |
47% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; In tetrahydrofuran; water; for 24h;Schlenk technique; Reflux; Inert atmosphere; | In a 100 mL Schlenk flask purged with nitrogen, 1.60 g (10.0 mmol) of 1,4-phenylenediboronic acid, 4.70 g of 2-bromopyridine (30.0 mmol), PdCl 2 (dppf)163 mg (2 molpercent), potassium carbonate 4.10 g (30.0 mmol), water 15 mL and tetrahydrofuran 15 mL were charged and reactedunder reflux conditions for 24 hours. After the reaction, it was separated and extracted with chloroform / water, concentrated andthen isolated by column chromatography using chloroform as a developing solvent to obtain 1,4-bis (2-pyridyl) benzene (6-1) 1.10 g (4.74 mmol) as a white solid in 47percent yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tetrakis(triphenylphosphine) palladium(0); Aliquat 336; potassium carbonate; In 1,4-dioxane; water; for 24h;Inert atmosphere; Reflux; | 15.00 g (63.44 mmol) 1-bromo-4-chloro-2-nitrobenzene and 5.00 g (30.17 mmol) 1 ,4-phenyldiboronic acid were dissolved in 215.0 ml of dioxane. Then, a few drops of Aliquat 336 and 85.0 ml of an aqueous K2C03 (2 M) were added. After degassing by argon bubbling, 0.70 g (0.61 mmol) of tetrakis(triphenylphosphine)palladium(0) were added. The reaction mixture was heated to reflux for 24 h. After cooling, the reaction mixture was poured on ice. 10.35 g (26.55 mmol) of a yellow precipitate which formed were collected, washed with methanol and used without further purification for the next step (88 percent). 1H NMR (250 MHz, CD2CI2): delta 7.92 (d, J = 2.1 , 2H), 7.67 (dd, J = 2.2, 8.3, 2H), 7.48 (d, J = 8.3, 2H), 7.38 (s, 4H). 13C NMR (75 MHz, CD2CI2): delta 149.89, 137.36, 134.88, 134.60, 133.79, 133.27, 128.89, 124.98. MS (FD, 8kV): m/z (percent) = 387.1 (100.0 percent, M+), (calc. Ci8H10CI2N2O4 = 389.91 g/mol). Elemental Analysis: found 56.56 percent C, 3.09 percent H, 6.53 percent N - calc. 55.55 percent C, 2.59 percent H, 7.20 percent N. |
52% | Example 1Preparation of 1,4-Bis(2'-nitro-4'-chlorophenyl)benzeneshows the reaction scheme for synthesis of 1,4-Bis(2'-nitro-4'-chlorophenyl)benzene.A one liter flask charged with 1-bromo-4-chloro-2-nitrobenzene (91.76 g, 388.0 mmol), 1,4-phenylenebisboronic acid (32.16 g, 194.0 mmol), potassium carbonate (55.28 g, 400.0 mmol), benzyltriethylammonium chloride (1000 mg, 4.4 mmol), PPh3 (1.20 g, 4.56 mmol), and Pd(PPh3)4 (1.20 g, 1.08 mmol) was flushed with nitrogen.Acetonitrile (300 mL) and water (150 mL) was then added.After stirring at room temperature (RT) under nitrogen for 5 minutes, the mixture was heated to and maintained at reflux (oil bath temp 90° C.) for 68 hours.The mixture was allowed to cool to room temperature and poured into 10percent HCl solution (400 mL) then filtered off the precipitate.The precipitate was washed with water (150 mL) and allowed to air dry.The dry powder was rinsed with cool THF and dried again to afford 39.25 g (52percent) of the desired product.1H NMR (500 MHz, DMF-d7) delta ppm: 8.24 (d, J=2.0 Hz, 2H), 7.94 (dd, J=8.3, 2.0 Hz, 2H), 7.57 (s, 4H), 7.73 (d, J=8.3 Hz, 2H). | |
With N-benzyl-N,N,N-triethylammonium chloride; potassium carbonate; triphenylphosphine;Pd(PPh3)4; In water; acetonitrile; | Example 1Preparation of 1,4-Bis(2'-nitro-4'-chlorophenyl)benzeneshows the reaction scheme for synthesis of 1,4-Bis(2'-nitro-4'-chlorophenyl)benzene.A one liter flask charged with 1-bromo-4-chloro-2-nitrobenzene (91.76 g, 388.0 mmol), 1,4-phenylenebisboronic acid (32.16 g, 194.0 mmol), potassium carbonate (55.28 g, 400.0 mmol), benzyltriethylammonium chloride (1000 mg, 4.4 mmol), PPh3 (1.20 g, 4.56 mmol), and Pd(PPh3)4 (1.20 g, 1.08 mmol) was flushed with nitrogen.Acetonitrile (300 mL) and water (150 mL) was then added.After stirring at room temperature (RT) under nitrogen for 5 minutes, the mixture was heated to and maintained at reflux (oil bath temp 90° C.) for 68 hours.The mixture was allowed to cool to room temperature and poured into 10percent HCl solution (400 mL) then filtered off the precipitate.The precipitate was washed with water (150 mL) and allowed to air dry.The dry powder was rinsed with cool THF and dried again to afford 39.25 g (52percent) of the desired product.1H NMR (500 MHz, DMF-d7) delta ppm: 8.24 (d, J=2.0 Hz, 2H), 7.94 (dd, J=8.3, 2.0 Hz, 2H), 7.57 (s, 4H), 7.73 (d, J=8.3 Hz, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 90℃; for 15.5h; | Example 11Synthesis of N-[(E)-3-(4'-boronic acid-biphenyl-2-yl)-2-methyl-acryloyl]guanidine<Step 1>Intermediate 1 (20 mg, 0.05 mmol) and 1,4-benzenediboronic acid (10 mg, 0.06 mmol) were dissolved in a mixed solution of dioxane and water (v/v=3/1, 2.4 mL). Pd(PPh3)4 (3.00 mg, 2.60 mumol) and Na2CO3 (21.0 mg, 0.152 mmol) were added to the solution and then stirred at 90° C. for 15.5 hours. After cooling it to room temperature, the solvent was eliminated in vacuo and then purified by reversed phase HPLC (0.1percent TFA in water/CH3CN) to obtain the compound of Example 11 (5.0 mg, 23percent).MS: 324 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34.2% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 90℃; for 6h;Inert atmosphere; | To a solution of (lR,3aS,5aR,5bR,7aR,l laR,l lbR,13aR,13bR)-benzyl5a,5b,8,8, 11 a-pentamethyl- 1 -(prop- 1 -en-2-yl)-9-(((trifluoromethyl)sulfonyl)oxy)- 2,3,3a,4,5,5a,5b,6,7,7a,8,l l,l la,l lb,12,13,13a,13b-octadecahydro-lH- cyclopenta[a]chrysene-3a-carboxylate (3.0 g, 4.43 mmol) in THF (100 mL) was added 1,4-benzenediboronic acid (1.469 g, 8.86 mmol) andtetrakis(triphenylphosphine)palladium(0) (0.259 g, 0.222 mmol). The resulting yellow mixture was purged with N2. Then, a solution of sodium carbonate (2.82 g, 26.6 mmol) in H2O (25.00 mL) was added and the reaction mixture was heated to reflux at 90 °C. After 6 h, the reaction mixture was cooled to rt, diluted with EtOAc (50 mL) and washed with H2O (50 mL). The aqueous layer was extracted with EtOAc (2 x 50 mL). The combined organic layer was filtered through celite pad, washed with brine, dried over MgS04, filtered and concentrated to afford a light brown solid. The crude material was absorbed onto silica gel (20 g), loaded onto a silica gel column and eluted with 3: 1 hexanes:EtOAc to give (4-((lR,3aS,5aR,5bR,7aR,l laS,l lbR,13aR,13bR)-3a- ((benzyloxy)carbonyl)-5a,5b,8,8, 11 a-pentamethyl- 1 -(prop- l-en-2-yl)- 2,3,3a,4,5,5a,5b,6,7,7a,8,l l,l la,l lb,12,13,13a,13b-octadecahydro-lH- cyclopenta[a]chrysen-9-yl)phenyl)boronic acid (983 mg, 34.2 percent) as a white solid. lH NMR (500MHz, CHLOROFORM-d) delta 8.18 - 8.14 (m, 2H), 7.43 - 7.38 (m, 4H), 7.38 - 7.35 (m, 1H), 7.31 - 7.29 (m, 1H), 5.37 - 5.34 (m, 1H), 5.17 (t, J=1.0 Hz, 2H), 4.77 (d, J=1.5 Hz, 1H), 4.64 (s, 1H), 3.08 (td, J=10.8, 4.7 Hz, 1H), 2.35 - 2.30 (m, 1H), 2.30 - 2.25 (m, 1H), 2.15 (dd, J=17.1, 6.1 Hz, 1H), 1.98 - 1.89 (m, 2H), 1.73 (s, 3H), 1.69 (d, J=3.7 Hz, 1H), 1.67 - 1.64 (m, 1H), 1.56 - 1.37 (m, 10H), 1.37 - 1.23 (m, 3H), 1.19 (d, J=13.1 Hz, 1H), 1.07 (dd, J=13.1, 4.3 Hz, 1H), 1.02 (s, 6H), 0.99 (br. s., 3H), 0.99 (br. s., 3H), 0.96 - 0.93 (m, 1H), 0.87 (s, 3H). 13C NMR (126MHz, CHLOROFORM-d) delta 175.8, 150.6, 148.41 - 148.39 (m, 1C), 148.3, 146.8, 136.5, 134.6, 129.7, 128.5, 128.2, 128.1, 123.7, 109.6, 65.7, 56.6, 52.9, 49.6, 49.4, 46.9, 42.4, 41.8, 40.5, 38.4, 37.5, 37.0, 36.3, 33.6, 32.1, 30.6, 29.6, 29.5, 25.7, 21.3, 21.1, 19.8, 19.4, 16.5, 15.6, 14.7 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With urea hydrogen peroxide adduct; In methanol; at 27 - 29℃; for 0.0833333h;Green chemistry; | General procedure: To a stirred solution of aryl/alkyl boronic acid (1 mmol) in methanol or acetonitrile solvent (1 ml) was added 1 equiv. of Urea-Hydrogen peroxide (UHP) (2.5 equiv for alkyl boronic acids) at room temperature and the progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with water and extracted with dichloromethane (DCM). The combined organic layer was dried over anhydrous sodium sulfate (Na2SO4), evaporated and subjected to silica gel column chromatography for further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 80℃; for 72h;Inert atmosphere; | (ii) Synthesis of hf,hf"-bis(4-octylphenyl)-[1, 1 'Alpha', 1 "-terphenyl]-2,2"-diamine; [00123] 2-bromo-N-(4-octylphenyl)aniline (652 mg, 1 .8 mmol), benzene-1 ,4- diboronic acid (100 mg, 0.6 mmol), Pd(PPh3)4 (70 mg, 0.06 mmol), Na2C03 (254 mg, 2.4 mmol) in toluene (20 ml_), EtOH (10 ml_), and H20 (10 ml_). The mixture was degassed by freeze and pump and stirred at 80 °C under argon atmosphere for 3 days. The mixture was extracted with dichloromethane (5 chi 50 ml_). The combined organic layers were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel (Pet ether- dichloromethane, 4:1 ) to afford the title compound (344 mg, 0.53 mmol; 86 percent) as a colourless solid. 1H NMR (CDCI3) delta 7.63 (s, 2H), 7.36 (m, 6H), 7.45-7.31 (m, 12H), 5.75 (s, 2H), 2.66 (t, J= 7.5 Hz, 4H), 1.71 (q, J= 6.5 Hz, 4H), 1 .39 (m, 20H), 1 .00 (t, J= 7 Hz, 6H). 13C NMR (CDCI3) delta 141.2, 140.8, 138.4, 136.5, 131 .0, 130.3, 130.0, 129.4, 129.3, 128.5, 120.6, 120.4, 1 19.5, 1 18.8, 1 17.1 , 35.4, 32.0, 31 .8, 29.7, 29.5, 29.4, 22.8, 14.3. Mass spectrum (APCI): m/z ([M+]) 636. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 80℃; for 72h;Inert atmosphere; | (ii) Synthesis of l ,lf"- henyl]-2,2"-diamine:[00116] 2-bromo-N-dodecylaniline (1 .1 1 g, 5.4 mmol), benzene-1 ,4-diboronic acid(0.18 g, 1 .8 mmol), Pd(PPh3)4 (0.13 g, 0.18 mmol), Na2C03 (0.42 g, 6.5 mmol) in toluene (10 mL), EtOH (5 mL), and H20 (5 mL). The mixture was degassed by freeze and pump and stirred at 80 °C under argon atmosphere for 3 days. The mixture was extracted with dichloromethane (5 chi 50 mL). The combined organic layers were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel (Pet ether- dichloromethane, 9:1 ) to afford the title compound (1.02 g, 1 .71 mmol; 95 percent) as a colourless solid.1 H NMR (CDCI3) delta 7.43 (s, 4H), 7.18 (t, J= 8 Hz, 2H), 7.09 (d, J= 8 Hz, 2H), 6.74 (m, 4H), 3.98 (s, 2H), 3.05 (t, J= 7 Hz, 4H), 1 .17 (m, 36 H), 0.80 (t, J= 7 Hz, 6H). Mass spectrum (APCI): m/z ([M+]) 597. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With potassium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,2-dimethoxyethane; water; at 100℃; for 18h; | 4-bromo-N,N'-diBoc-1 ,2-benzenediamine 2 (4.61 g, 1 1 .90 mmol), benzene-1 ,4- diyldiboronic acid 3 (0.988 g 5.96 mmol), potassium carbonate (2.396 g, 17.34 mmol) and PdCI2(dppf)-CH2CI2 adduct (0.487 g, 0.596 mmol) in 1 ,2- dimethoxyethane (26 mL) and water (8.67 mL) were heated in a oil bath at 100°C for 18 hours. The sample was filtered through celite, concentrated and the residue partitioned between brine and EtOAc. The organic layer was dried with MgSO4 filtered, concentrated and the product chromatographed on a silica column eluted with 0-40percent EtOAc in hexanes. The product was concentrated to yield tetrakis(1 ,1 -dimethylethyl) 1 ,1 ':4',1 "-terphenyl-3,3",4,4"- tetrayltetrakiscarbamate (3.20 g, 73percent) as a tan solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | With potassium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,2-dimethoxyethane; water; at 100℃; for 4h; | A mixture of benzene-1 ,4-diyldiboronic acid 3 (0.1 13 g, 0.684 mmol), methyl ((1 S)-1 -[(2S)-2-(5-bromo-7-fluoro-1 H-benzimidazol-2-yl)-1 -pyrrol idinyl]carbonyl}- 2-methylpropyl)carbamate 30 (0.604 g, 1 .369 mmol), PdCI2(dppf)-CH2CI2 adduct (0.1 12 g, 0.137 mmol) and potassium carbonate (0.284 g, 2.053 mmol) in DME (6 mL) and Water (1 .00 mL) was heated at 100 °C for 4h. The product was purified on a silica column using 0-20percent MeOH (2M NH3) / CH2CI2 gradient to afford 0.368g (0.461 mmol, 34percent) of the product as a dark yellow brown solid.1 H NMR (400 MHz, methanol-d4) delta 7.72 - 7.80 (m, 4H), 7.44 - 7.71 (m, 4H), 7.24 - 7.39 (m, 2H), 5.20 - 5.35 (m, 2H), 4.29 (d, J = 7.28 Hz, 2H), 3.88 - 4.12 (m, 4H), 3.68 (s, 8H), 1 .98 - 2.56 (m, 10H), 0.82 - 1 .06 (m, 12H)HRMS for C44H54N8O6 (M + H)+ calc: 799.3743, found: 799.370. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With C37H28N8O*2Cl(1-)*Pd(2+); potassium carbonate; In ethanol; at 70℃; for 2h; | General procedure: Arylhalide (5.0 mmol) and phenylboronic acid (5.0 mmol), K2CO3 (5.0 mmol) and X-Pd3L (0.005 molpercent Pd loading) were added to a solutionof 12 mL EtOH under ambient atmosphere. The mixture was stirred at 70 °C for 2 h. After cooling, H2O (10 mL) was added into the resultant mixture and the product was extracted by ethyl acetate (3 × 10 mL). The organic phase was combined and dried over Na2SO4. After removal of solvent, the product was dried at 60 °C. In most cases, the products are pure (analyzed by 1H NMR spectroscopy) because it is an equal stoichiometric reaction and the substrates are completely converted into product. If the product is impure, the purification can be performed ona silica gel chromatography (hexane:ether = 60:1 as an eluent). All products were confirmed by 1H and 13C NMR and compared with literatures (see SI). For the recycled experiment, the xerogel catalyst was recovered by centrifugation and washed with EtOH (3 × 4 mL) after reaction, then dried in air. |
87% | With palladium; potassium carbonate; In methanol; acetonitrile; at 20℃; for 2h; | General procedure: To a freshly prepared solution of PdNPs (10 mL, 0.02 mmol), required amount of K2CO3 (2 mmol) was added followed by aryldihalides/ arylhalide (1 mmol) and arylboronic acid (3 mmol)/diboronic acid (0.75 mmol). Then, the reaction mixture was stirred at room temperature in open atmosphere. The reaction was monitored by TLC and was stopped after the complete consumption of starting material. The desired product got precipitated out which was separated by filtration and extracted with chloroform. The chloroform layer was evaporated to get the terphenyl in pure state. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With palladium; potassium carbonate; In methanol; acetonitrile; at 20℃; for 3.5h; | General procedure: To a freshly prepared solution of PdNPs (10 mL, 0.02 mmol), required amount of K2CO3 (2 mmol) was added followed by aryldihalides/ arylhalide (1 mmol) and arylboronic acid (3 mmol)/diboronic acid (0.75 mmol). Then, the reaction mixture was stirred at room temperature in open atmosphere. The reaction was monitored by TLC and was stopped after the complete consumption of starting material. The desired product got precipitated out which was separated by filtration and extracted with chloroform. The chloroform layer was evaporated to get the terphenyl in pure state. |
85% | With C37H45ClN2O3PPd; potassium carbonate; In ethanol; water; at 80℃; for 6h;Inert atmosphere; Schlenk technique; | A 10-mL round-bottom flask was charged with the prescribe damount of catalyst, 1,4-benzenediboronic acid (0.5 mmol), N-heteroaryl halides (1.5 mmol), the selected base (1.5 mmol) and solvent (4 mL). The flask was placed in an oil bath and heated at 80 °C for 6 h, then cooled to room temperature and extracted with CH2Cl2. The crude products obtained from evaporation were purified by flash chromatography on silica gel. The products 5b?c, 5f, 5m [21], 5d [22], 5e [23], 5l [24] were known compounds and characterized by the comparison of data with those in the literature. The products 5a, 5g?k, 5n?o were new compounds and characterized by elemental analysis, IR, MS,1H and 13C NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With C37H45ClN2O3PPd; potassium carbonate; In ethanol; water; at 80℃; for 6h;Inert atmosphere; Schlenk technique; | A 10-mL round-bottom flask was charged with the prescribe damount of catalyst, 1,4-benzenediboronic acid (0.5 mmol), N-heteroaryl halides (1.5 mmol), the selected base (1.5 mmol) and solvent (4 mL). The flask was placed in an oil bath and heated at 80 °C for 6 h, then cooled to room temperature and extracted with CH2Cl2. The crude products obtained from evaporation were purified by flash chromatography on silica gel. The products 5b?c, 5f, 5m [21], 5d [22], 5e [23], 5l [24] were known compounds and characterized by the comparison of data with those in the literature. The products 5a, 5g?k, 5n?o were new compounds and characterized by elemental analysis, IR, MS,1H and 13C NMR. |
72% | With palladium; potassium carbonate; In methanol; acetonitrile; at 20℃; for 2h; | General procedure: To a freshly prepared solution of PdNPs (10 mL, 0.02 mmol), required amount of K2CO3 (2 mmol) was added followed by aryldihalides/ arylhalide (1 mmol) and arylboronic acid (3 mmol)/diboronic acid (0.75 mmol). Then, the reaction mixture was stirred at room temperature in open atmosphere. The reaction was monitored by TLC and was stopped after the complete consumption of starting material. The desired product got precipitated out which was separated by filtration and extracted with chloroform. The chloroform layer was evaporated to get the terphenyl in pure state. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With palladium; potassium carbonate; In methanol; acetonitrile; at 20℃; for 4.5h; | General procedure: To a freshly prepared solution of PdNPs (10 mL, 0.02 mmol), required amount of K2CO3 (2 mmol) was added followed by aryldihalides/ arylhalide (1 mmol) and arylboronic acid (3 mmol)/diboronic acid (0.75 mmol). Then, the reaction mixture was stirred at room temperature in open atmosphere. The reaction was monitored by TLC and was stopped after the complete consumption of starting material. The desired product got precipitated out which was separated by filtration and extracted with chloroform. The chloroform layer was evaporated to get the terphenyl in pure state. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With palladium; potassium carbonate; In methanol; acetonitrile; at 20℃; for 3h; | General procedure: To a freshly prepared solution of PdNPs (10 mL, 0.02 mmol), required amount of K2CO3 (2 mmol) was added followed by aryldihalides/ arylhalide (1 mmol) and arylboronic acid (3 mmol)/diboronic acid (0.75 mmol). Then, the reaction mixture was stirred at room temperature in open atmosphere. The reaction was monitored by TLC and was stopped after the complete consumption of starting material. The desired product got precipitated out which was separated by filtration and extracted with chloroform. The chloroform layer was evaporated to get the terphenyl in pure state. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With C37H45ClN2O3PPd; potassium carbonate; In ethanol; water; at 80℃; for 6h;Inert atmosphere; Schlenk technique; | A 10-mL round-bottom flask was charged with the prescribe damount of catalyst, 1,4-benzenediboronic acid (0.5 mmol), N-heteroaryl halides (1.5 mmol), the selected base (1.5 mmol) and solvent (4 mL). The flask was placed in an oil bath and heated at 80 °C for 6 h, then cooled to room temperature and extracted with CH2Cl2. The crude products obtained from evaporation were purified by flash chromatography on silica gel. The products 5b?c, 5f, 5m [21], 5d [22], 5e [23], 5l [24] were known compounds and characterized by the comparison of data with those in the literature. The products 5a, 5g?k, 5n?o were new compounds and characterized by elemental analysis, IR, MS,1H and 13C NMR. |
52% | With palladium; potassium carbonate; In methanol; acetonitrile; at 20℃; for 4h; | General procedure: To a freshly prepared solution of PdNPs (10 mL, 0.02 mmol), required amount of K2CO3 (2 mmol) was added followed by aryldihalides/ arylhalide (1 mmol) and arylboronic acid (3 mmol)/diboronic acid (0.75 mmol). Then, the reaction mixture was stirred at room temperature in open atmosphere. The reaction was monitored by TLC and was stopped after the complete consumption of starting material. The desired product got precipitated out which was separated by filtration and extracted with chloroform. The chloroform layer was evaporated to get the terphenyl in pure state. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(ll) dichloride; potassium carbonate; In methanol; toluene; at 55℃; for 1h;Inert atmosphere; | Argon was bubbled through a mixture of 1 ,4-benzenediboronic acid (24 mg, 0.15 mmol), intermediate X (151 mg, 0.32 mmol) and K2C03 (65 mg, 0.47 mmol) in toluene/MeOH (1 : 1, 4 ml). After 15 min PEPPSI-iPr? (5 mg, 0.007 mmol) was added and the mixture heated to 55 °C for 60 min. The reaction mixture was cooled to RT, diluted with CH2C12 (30 ml) and washed with water (30 ml). The aqueous layer was washed with CH2C12 (2 x 15 ml), the combined organic layers was evaporated to dryness to obtain the crude product. The residue was purified by flash chromatography using toluene/EtOAc (20:1? > 14: 1?9: 1) as eluent. Yield: 64 mg (51percent); Off- white solid. ¾ NMR (400 MHz, CDC13): delta 3.73 (s, 4H), 3.74 (s, 4H), 3.76 (s, 6H), 3.78 (s, 6H), 7.12 (d, J 5.0 Hz, 2H), 7.33 (d, J 5.0 Hz, 2H), 7.37 (s, 2H), 7.55 - 7.61 (m, 8H), 7.65 (s, 4H). The ester from above (64 mg, 0.08 mmol) was dissolved in dioxane (2 ml) and 2 M NaOH (2 ml) was added. After 2 hrs at 80 °C followed by 18 hrs at RT, the reaction mixture was diluted with water (20 ml) and acidified using 2 M HC1 (approx. 5 ml). The formed precipitate was isolated by centrifugation and washed three times with water. The material was dried under high vacuum for 2d. Yield: 50 mg (79percent); Yellow solid. 1H NMR (DMSO-i/6): 3.65 (s, 4H), 3.69 (s, 4H), 7.12 (d, J 5.3 Hz, 2H), 7.55 - 7.64 (m, 12H), 7.74 (s, 4H). HPLC: RT = 2.55 mm, 92percent (254 nm, 10- 40percent MeCN in 10 mM buffer, 3 mm, XBndge) and RT = 2.54 mm, 94percent (400 nm, 10-40percent MeCN in 10 mM buffer, 3 mm, XBndge). LC-MS : m/z = 808 (M + NH4+). |
51% | With [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(ll) dichloride; potassium carbonate; In methanol; toluene; at 55℃; for 1.25h;Inert atmosphere; | Argon was bubbled through a mixture of 1,4-benzenediboronic acid (24 mg, 0.15 mmol), intermediate X (151 mg, 0.32 mmol) and K2C03 (65 mg, 0.47 mmol) in toluene/MeOH (1 : 1, 4 ml). After 15 min PEPPSI-iPr? (5 mg, 0.007 mmol) was added and the mixture heated to 55 °C for 60 min. The reaction mixture was cooled to RT, diluted with CH2C12 (30 ml) and washed with water (30 ml). The aqueous layer was washed with CH2C12 (2 x 15 ml), the combined organic layers was evaporated to dryness to obtain the crude product. The residue was purified by flash chromatography using toluene/EtOAc (20: 1?14: 1?9: 1) as eluent. Yield: 64 mg (51percent); Off-white solid. 1H NMR (400 MHz, CDC13): delta 3.73 (s, 4H), 3.74 (s, 4H), 3.76 (s, 6H), 3.78 (s, 6H), 7.12 (d, J 5.0 Hz, 2H), 7.33 (d, J 5.0 Hz, 2H), 7.37 (s, 2H), 7.55 - 7.61 (m, 8H), 7.65 (s, 4H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(ll) dichloride; potassium carbonate; In methanol; toluene; at 60℃; for 2h;Inert atmosphere; | Argon was bubbled through a solution of intermediate Z (205 mg, 0.53 mmol) and 2,5-T thiophenediylbisboronic acid (44 mg, 0.26 mmol) in MeOH (3 ml) and toluene (3 ml) for 5 min. PEPPSI-iPr? (10 mg, 0.014 mmol) and K2C03 (220, 1.6 mmol) were added and the mixture heated to 60 °C for 2 hours. The mixture was then concentrated under vacuum and the crude material was dissolved in DCM with some MeOH. The solution was purified by flash chromatography using 40percent and 100percent EtOAc in iso-hexane as eluent. Yield: 104 mg (54percent); pale yellow solid. The ester from above (100 mg, 0.15 mmol) was added dioxane (4 ml) and 2 M NaOH (4 ml) and the mixture was heated at 80 °C for 90 min. The solution was cooled to r.t. and added 6 M HCl (2 ml). The formed precipitate was isolated by centrifugation and washed three times with water. The material was added some MeOH and the solvent was removed in vacuo. The yellow solid was then dried under high vacuum for 2 days. Yield: 59 mg (61percent); yellow solid. ? NMR (400 MHz, DMSO-i 6): delta 3.28 (s, 6H), 3.70 (s, 4H), 7.62 (s, 2H), 7.77 (s, 4H), 7.78 - 7.81 (m, 4H), 8.02 - 8.06 (m, 4H). Rt = 2.76 min, 95percent (254 nm, 10-40percent MeCN in 10 mM buffer, XBndge) Rt = 2.76 min, 95percent (400 nm, 10-40percent MeCN in 10 mM buffer, XBndge). LC-MS : m/z = 684 (M + NH^. |
54% | With [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(ll) dichloride; potassium carbonate; In methanol; toluene; at 60℃; for 2.08333h;Inert atmosphere; | Argon was bubbled through a solution of intermediate Z (205 mg, 0.53 mmol) and 2,5-T thiophenediylbisboronic acid (44 mg, 0.26 mmol) in MeOH (3 ml) and toluene (3 ml) for 5 min. PEPPSI-iPr? (10 mg, 0.014 mmol) and K2C03 (220, 1.6 mmol) were added and the mixture heated to 60 °C for 2 hours. The mixture was then concentrated under vacuum and the crude material was dissolved in DCM with some MeOH. The solution was purified by flash chromatography using 40percent and 100percent EtOAc in iso-hexane as eluent. Yield: 104 mg (54percent)); pale yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(ll) dichloride; potassium carbonate; In methanol; toluene; at 60℃; for 1h;Inert atmosphere; | Argon was bubbled through a mixture of 1,4-benzenediboronic acid (0.45 g, 2.72 mmol), intermediate B (1.34 g, 5.71 mmol) and K2CO3 (1.18 g, 8.57 mmol) in toluene/MeOH (1:1, 16 ml). After 15 min PEPPSI-iPr? (57 mg, 0.08 mmol) was added and the mixture heated at 60 °C for 60 min. The reaction mixture was cooled to RT, diluted with Et2O (35 ml), washed with water (40 ml), dried with MgSO4 (s), filtered and evaporated to dryness to obtain the crude product. The crude product was dissolved in hot acetone (15 ml) followed by drop wise addition of iso-hexane (17 ml) and stirred at 4 °C for 20 hrs. The obtained solid was filtered, washed with iso-hexane (6 ml), washed with Et2O (2 x 7 ml) and dried under vacuum. Yield: 0.48 g (46percent); white solid. 1H NMR (400 MHz, CDCl3): delta 3.70 (s, 4H), 3.73 (s, 6H), 7.10 (d, J 5.3 Hz, 2H), 7.30 (d, J 5.3 Hz, 2H), 7.53 (s, 4H). |
46% | With [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(ll) dichloride; potassium carbonate; In methanol; toluene; at 60℃; for 1h;Inert atmosphere; | Argon was bubbled through a mixture of 1,4-benzenediboronic acid (0.45 g, 2.72 mmol), intermediate B (1.34 g, 5.71 mmol) and K2C03 (1.18 g, 8.57 mmol) in toluene/MeOH (1 : 1, 16 ml). After 15 min PEPPSI-iPr? (57 mg, 0.08 mmol) was added and the mixture heated at 60 °C for 60 min. The reaction mixture was cooled to RT, diluted with Et20 (35 ml), washed with water (40 ml), dried with MgS04 (s), filtered and evaporated to dryness to obtain the crude product. The crude product was dissolved in hot acetone (15 ml) followed by drop wise addition of iso-hexane (17 ml) and stirred at 4 °C for 20 hrs. The obtained solid was filtered, washed with iso-hexane (6 ml), washed with Et20 (2 x 7 ml) and dried under vacuum. Yield: 0.48 g (46percent); white solid. 1H MR (400 MHz, CDC13): delta 3.70 (s, 4H), 3.73 (s, 6H), 7.10 (d, J 5.3 Hz, 2H), 7.30 (d, J 5.3 Hz, 2H), 7.53 (s, 4H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 83 - 85℃; for 4h;Inert atmosphere; | To a solution of 6-bromo-N,N-diphenylnaphthalen-2-amine (0.6415 g, 1.70 mmols) and 1,4- phenyldiboronic acid (0.144 g, 0.869 mmols) in toluene (10.5 mL) and ethanol (6.0 mL) was added a solution of sodium carbonate (0.87 g, 8 mmols) in water (8.0 mL). The solution was degassed with nitrogen, and then tetrakis(triphenylphosphine)palladium (0.165 g, 0.143 mmol) was added. The solution was again degassed with nitrogen and then heated to reflux in an oil bath at 83-85 °C and stirred for 4 hours. The reaction solution was then poured into ethyl acetate and water. A precipitate was filtered off, and the organic layer was dried over sodium sulfate, concentrated, and the crude product was chromatographed (0.5-1.0percent ethyl acetate in hexanes, silica gel) to give the title compound (0.377 g, 66percent) as a yellow, crystalline compound, m.p. 225-226 °C: 1H NMR (400 MHz, CDC13) delta 8.04 (s, 2H), 7.82 (s, 4H), 7.77 (d, J= 9.2 Hz, 2H), 7.74 (dd, J= 8.8, 1.6 Hz, 2H), 7.68 (d, J= 8.8 Hz, 2H), 7.46 (d, J= 2.0 Hz, 2H), 7.33 (dd, J = 8.8, 2.4 Hz, 2H), 7.27-7.32 (m, 8H), 7.17 (d, J= 8.4 Hz, 8H), 7.07 (t, J= 7.2 Hz, 2H); 13C NMR (100 MHz, CDC13) delta 147.7, 145.6, 139.8, 136.5, 133.6, 130.1, 129.3, 129.1, 127.5, 127.4, 125.7, 125.3, 124.7, 124.4, 123.0, 119.6; LCMS (M+H)+ Calc'd for C50H37N2 665.2957, found 665.2967. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In tetrahydrofuran; water; N,N-dimethyl-formamide; at 70℃; for 48h;Inert atmosphere; Sealed tube; | Compound 12a (400 mg, 0.748 mmol), Pd(PPh3)4 (86 mg, 74.8 mol) and benzene-1,4-diboronic acid (59 mg, 0.36 mmol) were filled in a sealed tube and flushed with argon. THF (2 mL), DMF (8 mL) and 2 M aq. Na2CO3 solution (1.5 mL) were added and the mixture was stirred for 48 h at 70 °C. The solution was cooled to rt, brine (20 mL) was added and the aqueous layer extracted with ethyl acetate (3 x 80 mL). The combined organic layers were dried with Na2SO4, filtered and the solvents removed in vacuo. The crude product was purified by column chromatography (silica gel, hexanes/EtOAc 3:2) to yield 21 (296 mg, 84percent) as a yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With sodium azide; copper(ll) sulfate pentahydrate; In methanol; at 20℃; for 40h; | To a solution of sodium azide (5.00 mmol; 0.32 g) and copper(II) sulfate pentahydrate (0.40 mmol; 99.80 mg) in methanol (5 mL), 1,4-phenylene diboronic acid (2.00 mmol; 0.33 g) was added. The reaction mixture was left stirring at room temperature for 40 h. The solvent was removed under reduced pressure and the residue treated with petroleum ether. The solvent was removed to give the 1,4-diazidobenzene (0.21 g; 67percent) as an orange solid. Mp 79.0-82.0 °C (from petroleum ether). IR (Nujol): nu=2954 (C-H), 2924 (C-H), 2854 (C-H), 2107 (N3) cm-1. 1H NMR (400 MHz, CDCl3): delta=7.02 (4H, s, ArH) ppm. 13C NMR (100.6 MHz, CDCl3): delta=120.34 (CH), 136.67 (C) ppm. C6H4N6 (160.14): calcd C 45.00, H 2.52, N 52.48; found C 45.12, H 2.70, N 52.25. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | General procedure: Aryl boronic acid (1.0 mmol), CuI (5 molpercent),amide (3.0 mmol), and DMSO (1.0 mL) were added to a reactionvial, and the mixture was stirred at room temperature for10 min. A 70percent aqueous solution of TBHP (1.1 mmol) was addedto the reaction mixture dropwise over 5 min. The reaction vialwas then immersed in a preheated oil bath and the progress ofreaction was followed by TLC. Upon completion of reaction, thecooled mixture was partitioned between water and ethyl acetate.The aqueous layer was further extracted with ethyl acetate,and the combined organic layers were washed with brine,dried over Na2SO4, filtered, and concentrated in vacuo. Theresidue was purified by column chromatography on silica gel(hexane?ethyl acetate) to give the desired N-aryl lactam |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With C37H45ClN2O3PPd; potassium carbonate; In ethanol; water; at 80℃; for 6h;Inert atmosphere; Schlenk technique; | A 10-mL round-bottom flask was charged with the prescribe damount of catalyst, 1,4-benzenediboronic acid (0.5 mmol), N-heteroaryl halides (1.5 mmol), the selected base (1.5 mmol) and solvent (4 mL). The flask was placed in an oil bath and heated at 80 °C for 6 h, then cooled to room temperature and extracted with CH2Cl2. The crude products obtained from evaporation were purified by flash chromatography on silica gel. The products 5b?c, 5f, 5m [21], 5d [22], 5e [23], 5l [24] were known compounds and characterized by the comparison of data with those in the literature. The products 5a, 5g?k, 5n?o were new compounds and characterized by elemental analysis, IR, MS,1H and 13C NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With C37H45ClN2O3PPd; potassium carbonate; In ethanol; water; at 80℃; for 6h;Inert atmosphere; Schlenk technique; | A 10-mL round-bottom flask was charged with the prescribe damount of catalyst, 1,4-benzenediboronic acid (0.5 mmol), N-heteroaryl halides (1.5 mmol), the selected base (1.5 mmol) and solvent (4 mL). The flask was placed in an oil bath and heated at 80 °C for 6 h, then cooled to room temperature and extracted with CH2Cl2. The crude products obtained from evaporation were purified by flash chromatography on silica gel. The products 5b?c, 5f, 5m [21], 5d [22], 5e [23], 5l [24] were known compounds and characterized by the comparison of data with those in the literature. The products 5a, 5g?k, 5n?o were new compounds and characterized by elemental analysis, IR, MS,1H and 13C NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With C37H45ClN2O3PPd; potassium carbonate; In ethanol; water; at 80℃; for 6h;Inert atmosphere; Schlenk technique; | A 10-mL round-bottom flask was charged with the prescribe damount of catalyst, 1,4-benzenediboronic acid (0.5 mmol), N-heteroaryl halides (1.5 mmol), the selected base (1.5 mmol) and solvent (4 mL). The flask was placed in an oil bath and heated at 80 °C for 6 h, then cooled to room temperature and extracted with CH2Cl2. The crude products obtained from evaporation were purified by flash chromatography on silica gel. The products 5b?c, 5f, 5m [21], 5d [22], 5e [23], 5l [24] were known compounds and characterized by the comparison of data with those in the literature. The products 5a, 5g?k, 5n?o were new compounds and characterized by elemental analysis, IR, MS,1H and 13C NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With C37H45ClN2O3PPd; potassium carbonate; In ethanol; water; at 80℃; for 6h;Inert atmosphere; Schlenk technique; | A 10-mL round-bottom flask was charged with the prescribe damount of catalyst, 1,4-benzenediboronic acid (0.5 mmol), N-heteroaryl halides (1.5 mmol), the selected base (1.5 mmol) and solvent (4 mL). The flask was placed in an oil bath and heated at 80 °C for 6 h, then cooled to room temperature and extracted with CH2Cl2. The crude products obtained from evaporation were purified by flash chromatography on silica gel. The products 5b?c, 5f, 5m [21], 5d [22], 5e [23], 5l [24] were known compounds and characterized by the comparison of data with those in the literature. The products 5a, 5g?k, 5n?o were new compounds and characterized by elemental analysis, IR, MS,1H and 13C NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With C37H45ClN2O3PPd; potassium carbonate; In ethanol; water; at 80℃; for 6h;Inert atmosphere; Schlenk technique; | A 10-mL round-bottom flask was charged with the prescribe damount of catalyst, 1,4-benzenediboronic acid (0.5 mmol), N-heteroaryl halides (1.5 mmol), the selected base (1.5 mmol) and solvent (4 mL). The flask was placed in an oil bath and heated at 80 °C for 6 h, then cooled to room temperature and extracted with CH2Cl2. The crude products obtained from evaporation were purified by flash chromatography on silica gel. The products 5b?c, 5f, 5m [21], 5d [22], 5e [23], 5l [24] were known compounds and characterized by the comparison of data with those in the literature. The products 5a, 5g?k, 5n?o were new compounds and characterized by elemental analysis, IR, MS,1H and 13C NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With C37H45ClN2O3PPd; potassium carbonate; In ethanol; water; at 80℃; for 6h;Inert atmosphere; Schlenk technique; | A 10-mL round-bottom flask was charged with the prescribe damount of catalyst, 1,4-benzenediboronic acid (0.5 mmol), N-heteroaryl halides (1.5 mmol), the selected base (1.5 mmol) and solvent (4 mL). The flask was placed in an oil bath and heated at 80 C for 6 h, then cooled to room temperature and extracted with CH2Cl2. The crude products obtained from evaporation were purified by flash chromatography on silica gel. The products 5b-c, 5f, 5m [21], 5d [22], 5e [23], 5l [24] were known compounds and characterized by the comparison of data with those in the literature. The products 5a, 5g-k, 5n-o were new compounds and characterized by elemental analysis, IR, MS,1H and 13C NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With C37H45ClN2O3PPd; potassium carbonate; In ethanol; water; at 80℃; for 6h;Inert atmosphere; Schlenk technique; | A 10-mL round-bottom flask was charged with the prescribe damount of catalyst, 1,4-benzenediboronic acid (0.5 mmol), N-heteroaryl halides (1.5 mmol), the selected base (1.5 mmol) and solvent (4 mL). The flask was placed in an oil bath and heated at 80 °C for 6 h, then cooled to room temperature and extracted with CH2Cl2. The crude products obtained from evaporation were purified by flash chromatography on silica gel. The products 5b?c, 5f, 5m [21], 5d [22], 5e [23], 5l [24] were known compounds and characterized by the comparison of data with those in the literature. The products 5a, 5g?k, 5n?o were new compounds and characterized by elemental analysis, IR, MS,1H and 13C NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With C37H45ClN2O3PPd; potassium carbonate; In ethanol; water; at 80℃; for 6h;Inert atmosphere; Schlenk technique; | A 10-mL round-bottom flask was charged with the prescribe damount of catalyst, 1,4-benzenediboronic acid (0.5 mmol), N-heteroaryl halides (1.5 mmol), the selected base (1.5 mmol) and solvent (4 mL). The flask was placed in an oil bath and heated at 80 °C for 6 h, then cooled to room temperature and extracted with CH2Cl2. The crude products obtained from evaporation were purified by flash chromatography on silica gel. The products 5b?c, 5f, 5m [21], 5d [22], 5e [23], 5l [24] were known compounds and characterized by the comparison of data with those in the literature. The products 5a, 5g?k, 5n?o were new compounds and characterized by elemental analysis, IR, MS,1H and 13C NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With C37H45ClN2O3PPd; potassium carbonate; In ethanol; water; at 80℃; for 6h;Inert atmosphere; Schlenk technique; | A 10-mL round-bottom flask was charged with the prescribe damount of catalyst, 1,4-benzenediboronic acid (0.5 mmol), N-heteroaryl halides (1.5 mmol), the selected base (1.5 mmol) and solvent (4 mL). The flask was placed in an oil bath and heated at 80 °C for 6 h, then cooled to room temperature and extracted with CH2Cl2. The crude products obtained from evaporation were purified by flash chromatography on silica gel. The products 5b?c, 5f, 5m [21], 5d [22], 5e [23], 5l [24] were known compounds and characterized by the comparison of data with those in the literature. The products 5a, 5g?k, 5n?o were new compounds and characterized by elemental analysis, IR, MS,1H and 13C NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With C37H45ClN2O3PPd; potassium carbonate; In ethanol; water; at 80℃; for 6h;Inert atmosphere; Schlenk technique; | A 10-mL round-bottom flask was charged with the prescribe damount of catalyst, 1,4-benzenediboronic acid (0.5 mmol), N-heteroaryl halides (1.5 mmol), the selected base (1.5 mmol) and solvent (4 mL). The flask was placed in an oil bath and heated at 80 °C for 6 h, then cooled to room temperature and extracted with CH2Cl2. The crude products obtained from evaporation were purified by flash chromatography on silica gel. The products 5b?c, 5f, 5m [21], 5d [22], 5e [23], 5l [24] were known compounds and characterized by the comparison of data with those in the literature. The products 5a, 5g?k, 5n?o were new compounds and characterized by elemental analysis, IR, MS,1H and 13C NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 2h; | 2-bromo-naphthalene (2.07g, 10mmol), benzene-1,4-diBoronic acid(2.49g, 15mmol), Pd (PPh3) 4 (0.58 g, 0.5mmol), potassium carbonate (4.15g, 30mmol) and THF: H2O = 2:1 solution dissolved in 200ml 80 After 2 hours reflux agitation. Thereafter it was added and extracted three times with 40ml ethyl ether H2O40ml drying the obtained organic layer with magnesium sulfate, and separating the residue obtained by evaporating the solvent was subjected to silica gel column chromatography purification Intermediate B-1 (1.98g, 80% yield) It was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 2h; | Chloro-Triphenyl silane(2.94g, 10mmol), benzene-1,4-dibo acid (2.49g, 15mmol), Pd (PPh3) 4 (0.58 g, 0.5mmol), potassium carbonate (4.15g, 30mmol) and THF: H2O = 2: was dissolved in 1 200ml solution was stirred for 2 hours under reflux at 80 . Thereafter it was added three times with 40ml ethyl ether H2O40ml extract obtained by drying the organic layers with magnesium sulfate, and separating the residue obtained by evaporating the solvent was subjected to silica gel column chromatography purification Intermediate B-2 (3.04g, 80percent yield) It was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In methanol; water; for 12h;Reflux; Inert atmosphere; | 1,4-Phenylene diboronic acid (1.0 g, 6.03 mmol) was dissolved in 1,2-dimethoxyethanol (100 mL) and methanol (10 mL)4-Bromoanisole (1.24 g, 6.64 mmol) and <strong>[104197-14-0]2,6-difluoro-4-bromoanisole</strong> (1.48 g, 6.64 mmol) were added dropwise to the above mixed solution,2 M aqueous potassium carbonate solution (20 mL) was added and degassed. Palladium tetrakis (triphenylphosphine) (349 mg, 0.30 mmol) was added to the mixed solution, and the mixture was refluxed under nitrogen atmosphere for 12 hours.An excessive amount of distilled water was added to the reaction solution to terminate the reaction,After extracting with dichloromethane, the solvent was concentrated under reduced pressure. The mixture obtained above was purified by column chromatography to give the desired compound (913 mg, 45%) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In methanol; water; for 12h;Reflux; Inert atmosphere; | 1,4-phenylene diboronic acid (1.0 g, 6.03 mmol)1,2-Dimethoxyethanol (100 mL)And methanol (10 mL) was addedAfter dissolution,4-Bromoanisole (1.24 g, 6.64 mmol) and <strong>[406482-22-2]2,3-difluoro-4-bromoanisole</strong> (1.48 g, 6.64 mmol) were added dropwise to the mixed solution,2 M aqueous potassium carbonate solution (20 mL) was added and degassed.To the mixed solution, palladium tetrakis (triphenylphosphine)(349 mg, 0.30 mmol), and the mixture was refluxed under nitrogen atmosphere for 12 hours.An excessive amount of distilled water was added to the reaction solution to terminate the reaction,After extraction with dichloromethane, the solvent was concentrated under reduced pressure,The residue was purified by column chromatography to give the desired compound (827 mg, 42%) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.6% | under the protection of nitrogen, into 200 ml THF, 15 . 0g (0.62 muM) magnesium,1.0g(0.004mol)I2, slowly dropping containing 68.4g (0.29 muM) of the two 1, 4 - bromobenzene 300 ml THF solution, adds by drops in 30 °C reaction 3h, cooling to -70 °C, slowly dropping boric acid three methyl ester (78.5 ml, 0 . 72 muM) and 300 ml THF of a mixed solution of the, completion of the dropping, for -70 °C reaction 1h, Slowly to room temperature stirring 12h. Adding 2.5M HCl950ml fast stirring 15min, filtering, with 300 ml hexane washing three times, vacuum drying, the white solid obtained 40.7g, yield of 84.6percent. | |
47% | Compound m (8.87 g, 37.6 mmol) was dissolved in tetrahydrofuran (140 mL), and hexane solvent and 2.5 M n-butyl lithium (18 mL, 45.1 mmol) were added dropwise at -78 ° C, and then stirred for 1 hour.After slowly adding trimethyl borate (13 mL, 56.4 mmol),Stir for 2 h. It was further neutralized by dropwise addition of 2M hydrochloric acid, and the product was extracted with ethyl acetate and water.Recrystallization from dichloromethane and hexane gave compound n (2.93 g, 47percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,2-dimethoxyethane; water; for 14h;Reflux; | A mixture of 1,4-phenylenediboronic acid (80mg, 0.48mmol) and <strong>[685517-71-9]<strong>[685517-71-9]2,6-difluoro-4-iodopyridin</strong>e</strong> (233mg, 0.97mmol) was added to a suspension of Pd (PPh3)4 (56mg, 0.048mmol) in 1,2-dimethoxyethane (5mL) and aqueous Na2CO3 (1.0mL, 2mol/L). The mixture was subsequently maintained at reflux for 14h, allowed to cool and then poured into H2O (20mL) and extracted with CH2Cl2 (3×15mL). The organic extracts were dried (MgSO4), concentrated in vacuo and the residue was purified by column chromatography (CH2Cl2/pentane=1:9, v/v) to give the product as a white powder (113mg, 77%). 1H NMR (400MHz, CDCl3): delta 7.77 (s, 4H), 7.07 (s, 4H). 19F NMR (376MHz, CDCl3): delta -67.6. HRMS m/z calcd. for C16H8F4N2Na [M+Na+]: 304.0624, found: 304.0624. MP: 308-310C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 80℃; for 18h;Inert atmosphere; | General procedure: The synthesis of 1,4-bis-(8-benzyloxyquinolin-5-yl)benzene 15 will be used as representative example for the synthesis of bis-8-tosyloxyquinolines 17. 5-Bromo-8-benzyloxyquinoline 14 (314 mg, 1 mmol, 1 equiv), benzene-1,4-diboronic acid (82.8 mg, 0.5 mmol, 0.5 equiv), sodium carbonate (217 mg, 2.05 mmol, 2.05 equiv) and tetrakis(triphenylphosphine)palladium(0) (35 mg, 0.06 mmol, 0.06 equiv) were added to a flask (50 mL). Meanwhile, a solvent mixture of toluene/ethanol/water (3/1/1, 15 mL/5 mL/5 mL) was degassed under argon atmosphere by a freeze-thaw procedure. The degassed solvent mixture was added to the reagents and the mixture was stirred for 18 hours at 80°C under argon atmosphere. When the reaction was finished, the mixture was cooled and the crude product was extracted with CH2Cl2 (25 mL) and water (25 mL). The organic fraction was washed three times with water (25 mL), dried (MgSO4) and evaporated to obtain the crude product. Recrystallization from CHCl3 yielded 1,4-bis-(8-benzyloxyquinolin-5-yl)benzene 15 in 52percent (141 mg, 0.26 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With diiodido[5-(4-methoxyphenyl)-1-methyl-3-(2-methylpropyl)-1H-imidazole-2-ylidene] pyridinepalladium; potassium carbonate; In toluene; at 120℃; under 10343.2 Torr; for 120h;Autoclave; | General procedure: A 45mL stainless steel autoclave equipped with a glass liner, gas inlet valve and pressure gauge was used for the carbonylative Suzuki coupling reaction. Palladium complex (0.010molpercent), aryl iodide (1.0mmol), arylboronic acid (1.2mmol), base (2.0mmol) and solvent (3.0mL) were added into the glass liner. The autoclave was vented three times with carbon monoxide and then pressurized to 200 psi of CO. The mixture was heated to the required temperature and maintained under stirring for the required time. After complete reaction, the mixture was cooled down to room temperature and CO excess was released under fume hood. The mixture was diluted with 5mL of water and extracted three times with 10mL ethyl acetate. The combined ethyl acetate extract was concentrated under reduced pressure in a rotavapor. The product was analyzed with GC and GC-MS. The spectral data of the diarylketones prepared in this study were in full agreement with those reported in literature [1,2,32?37] |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With diiodido[5-(4-methoxyphenyl)-1-methyl-3-(2-methylpropyl)-1H-imidazole-2-ylidene] pyridinepalladium; potassium carbonate; In toluene; at 120℃; under 10343.2 Torr; for 120h;Autoclave; | General procedure: A 45mL stainless steel autoclave equipped with a glass liner, gas inlet valve and pressure gauge was used for the carbonylative Suzuki coupling reaction. Palladium complex (0.010molpercent), aryl iodide (1.0mmol), arylboronic acid (1.2mmol), base (2.0mmol) and solvent (3.0mL) were added into the glass liner. The autoclave was vented three times with carbon monoxide and then pressurized to 200 psi of CO. The mixture was heated to the required temperature and maintained under stirring for the required time. After complete reaction, the mixture was cooled down to room temperature and CO excess was released under fume hood. The mixture was diluted with 5mL of water and extracted three times with 10mL ethyl acetate. The combined ethyl acetate extract was concentrated under reduced pressure in a rotavapor. The product was analyzed with GC and GC-MS. The spectral data of the diarylketones prepared in this study were in full agreement with those reported in literature [1,2,32?37] |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
9.8 g | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 6h;Inert atmosphere; Reflux; | Will 10 grams of 4-bromopyridine,11 grams of 1,4-benzenediboronic acid,20 grams of sodium carbonate,120 ml of toluene,80 ml of ethanol,40 ml of water was added to a 500 ml three-necked bottle.Under nitrogen protection,0.65g of Pd(pph3)4 was added,Heated to reflux,The reaction is complete after 6 hoursCooling,The solid obtained by suction filtrationWash with ethyl acetate,Get the product,9.8 grams. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75.3% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; at 85℃; for 24h;Inert atmosphere; | Bromo-2,4,5-trimethyl-benzene (1) (2.64 g, 13.26 mmol), benezene- 1 ,4-diboronic acid (3) (1.00 g, 6.03 mmol) and a catalytic amount of tetrakis(triphenylphosphine)palladium(0) (0.10 g, 0.08 mmol) were added into a two-necked flask fitted with an Allihn condenser. The system was degassed and refilled with nitrogen three times. Then, 60 mL of distilled THF was injected, followed with an aqueous solution of potassium carbonate (0.15 g, 20 mL). After stifling at 85 C for 24 h, the mixture was extracted with DCM. The organic layer was collected and washed with deionized water and brine, and dried over anhydrous sodium sulfate. After filtration, the filtrate was evaporated under reduced pressure, and the crude product was purified by silica gel column chromatography using hexanelDCM (5/1, v/v) as eluent. A white powder of TPh-TM was obtained in 75.3% yield (1.42 g, 4.52 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | In tetrahydrofuran; for 27h;Reflux; | A mixture of 4b (151.6 mg, 1.00 mmol) and 1,4-benzenediboronic acid 6 (82.8 mg, 0.50 mmol) in dry THF (3.0 mL) was refluxed for 27 h, and then the solvent was distilled off under reduced pressure. The residue was purified by chromatography on silica gel (ethyl acetate/CHCl3 = 1/1) to give 7 (63.1 mg, 32%) as a brown solid: mp 229.9-230.2 C; 1H NMR (500 MHz, CDCl3) delta 7.80 (s, 4 H), 7.15-7.12 (m, 4 H), 6.92 (dt, J = 1.1 and 7.5 Hz, 2 H), 6.74 (d, J = 7.7 Hz, 2 H), 5.86 (br s, 2 H), 1.68 (s, 12 H); 13C NMR (126 MHz, CDCl3) delta 137.6, 131.9, 130.9, 127.7, 124.9, 121.2, 115.6, 74.8, 31.4; IR (KBr) 3408, 2972, 1560, 1519, 1502, 1472, 1419 cm-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrahydrofuran; at 20℃; for 0.5h; | A mixture of 4b (151 mg, 1.00 mmol), 1,4-benzenediboronic acid 6 (82.9 mg, 0.500 mmol), and catechol 8 (110 mg, 1.00 mmol) in dry THF (5.0 mL) was stirred at room temperature for 30 min, and then the solvent was distilled off under reduced pressure. The product ratio was determined by the 1H NMR spectrum of the crude product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrahydrofuran; for 0.5h;Reflux; | A mixture of 4b (75.3 mg, 0.500 mmol), 1,4-benzenediboronic acid 6 (41.6 mg, 0.251 mmol), and catechol 8 (55.1 mg, 0.500 mmol) in dry THF (2.5 mL) was refluxed for 30 min. The reaction mixture was cooled to room temperature, and then the solvent was distilled off under reduced pressure. The product ratio was determined by the 1H NMR spectrum of the crude product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With 1-(3-phenylpropyl)-3-pentylbenzimidazolium bromide; palladium diacetate; potassium carbonate; In water; N,N-dimethyl-formamide; at 100℃; for 0.0833333h;Microwave irradiation; | General procedure: Bromobenzene (1 mmol) or 1-bromonaphthalene (1 mmol), phenylboronic acid (1 mmol), or benzene-1,4-diboronic acid (0,5 mmol), K2CO3 (2 mmol), Pd(OAc)2 (1 molpercent), 1a?1h (2 molpercent), and DMF (3 mL)-H2O(3 mL) were added to an apparatus of microwave equipment. The mixture was stirred and heated at 100 °C by microwave irradiation (300 W) for 5 min. After the completion of the reaction, the product was extracted with ethyl acetate from the mixture. Then the purification was done by crystallization from ethyl acetate/n-hexane(1:1). The isolated yield was calculated. The product structures were determined by 1 H-NMR, 13 C-NMR, and LC-MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With Pd-132; In ethanol; water; toluene; at 85 - 90℃; for 3h;Inert atmosphere; Alkaline conditions; | Add 16 · 56g of potassium carbonate to the four-necked flask,22 · 3g (0 · lmol) 3-bromo-7-aminoquinoline,0 · 10 g of Pd-132, 100 g of ultrapure water and 120 mL of toluene.Turn on mechanical agitation, and replace the system with N2 for 3 times.The temperature of the system was raised to 85-90 ° C to reflux.8.25 g (0.05 mol) of 1,4-diphenylboronic acid was weighed and dissolved in 60 mL of absolute ethanol, and slowly added dropwise to the reaction system, and the temperature of the control system was refluxed at 85-90 ° C.After the addition was completed, the system continued to reflux for 3 h.Then cool down and stop stirring.Add 200 mL of toluene to the system.After stirring at room temperature for 10 min, it was poured into a separatory funnel and allowed to stand for separation. The aqueous phase was poured into a flask. After adding 200 mL of toluene, the extraction was continued once, and the aqueous phase was discarded after standing.Combine the organic phases. The organic phase was then concentrated to give a crude solid.After recrystallization from a toluene/ethanol mixed solvent,A solid product of 15.9 g was obtained in a yield of 88percent. |
Tags: 4612-26-4 synthesis path| 4612-26-4 SDS| 4612-26-4 COA| 4612-26-4 purity| 4612-26-4 application| 4612-26-4 NMR| 4612-26-4 COA| 4612-26-4 structure
[ 172975-69-8 ]
3,5-Dimethylphenylboronic acid
Similarity: 0.81
[ 55499-44-0 ]
2,4-Dimethylphenylboronic acid
Similarity: 0.81
[ 172975-69-8 ]
3,5-Dimethylphenylboronic acid
Similarity: 0.81
[ 55499-44-0 ]
2,4-Dimethylphenylboronic acid
Similarity: 0.81
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