* 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.
Reference：
[1] European Journal of Organic Chemistry, 2007, # 20, p. 3271 - 3276
[2] Journal of Organic Chemistry, 2006, vol. 71, # 20, p. 7854 - 7857
[3] Patent: EP1972338, 2008, A1,
2
[ 51760-21-5 ]
[ 73183-34-3 ]
[ 944392-68-1 ]
Yield
Reaction Conditions
Operation in experiment
72.5%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 100℃; for 12.5 h; Inert atmosphere
5-bromo-1,3-benzenedicarboxylic acid dimethyl ester (5. 4 g, 19.8 mmol), boronic acid pinacol ester (6.0 g, (7.5 g, 57.2 mmol), placed in 250 mL three-necked flask, add anhydrous 1,4-dioxane (50 mL) as solvent, protected by N2, 0 • 5 h Pd (dppf) 2C12 ( • 2 g, 0 • 27 mmol), the temperature was raised to 100 ° C for 12 h, the temperature dropped to room temperature and the excess of 1,4-dioxane was distilled off. H2O (20 mL ), Extracted with ethyl acetate (30 mL) and extracted three times. The organic phase was collected and dried over anhydrous Na2SO3. The filtrate was evaporated to dryness to give the crude product. The crude product was purified by silica gel column chromatography (eluent: petroleum ether / acetic acid Ethyl ester = 94/6) to afford white powder B (4.59 g) in 72percent yield.
Reference：
[1] Chemical Communications, 2015, vol. 51, # 40, p. 8508 - 8511
[2] Journal of the American Chemical Society, 2013, vol. 135, # 32, p. 11887 - 11894
[3] Patent: CN105237337, 2016, A, . Location in patent: Paragraph 0021
[4] Chemical Communications, 2013, vol. 49, # 20, p. 2043 - 2045
[5] Inorganic Chemistry, 2015, vol. 54, # 9, p. 4377 - 4381
[6] CrystEngComm, 2017, vol. 19, # 11, p. 1464 - 1469
[7] Chinese Journal of Chemistry, 2017, vol. 35, # 8, p. 1289 - 1293
3
[ 51839-15-7 ]
[ 73183-34-3 ]
[ 944392-68-1 ]
Reference：
[1] Journal of the American Chemical Society, 2012, vol. 134, # 49, p. 20110 - 20116
[2] Journal of the American Chemical Society, 2018, vol. 140, # 25, p. 7773 - 7777
[3] Journal of Organic Chemistry, 2006, vol. 71, # 20, p. 7854 - 7857
[4] European Journal of Organic Chemistry, 2007, # 20, p. 3271 - 3276
[5] Organic and Biomolecular Chemistry, 2011, vol. 9, # 18, p. 6284 - 6292
[6] RSC Advances, 2013, vol. 3, # 6, p. 1902 - 1915
[7] Chemical Communications, 2013, vol. 49, # 30, p. 3110 - 3112
[8] Patent: EP1972338, 2008, A1, . Location in patent: Page/Page column 13-14
With bis(1,5-cyclooctadiene)diiridium(I) dichloride; 1-(4,4'-di-tert-butyl-[2,2'-bipyridin]-6-yl)-2-(dimethyl(phenyl)silyl)-2,3-dihydro-1H-benzo[d][1,3,2]diazaborole;Inert atmosphere; Schlenk technique; Sealed tube;
General procedure: B2pin2, [IrCl(COD)]2 (1.0 mol%), preligand 1 (2.0 mol%), and (hetero)arene (0.2 mmol, ifsolid) were placed in a dried Schlenk flask (15 mL in volume) equipped with a stirring bar. Afterevacuating and refilling the flask with dry nitrogen three times, (hetero)arene (0.2 mmol, if liquid)and methoxycyclopentane (CAPE, 0.5 mL) were added with syringes under a stream of nitrogen.The resulting mixture was stirred at the corresponding temperature for the assigned time. After cooling to room temperature, the reaction mixture was concentrated and then purified by columnchromatography on silica gel to give the target product (The spectra data for the borylated compoundscan be seen in the Supplementary Material).
dimethyl 4-(3,5-bis(methoxycarbonyl)phenyl)pyridine-2,6-dicarboxylate[ No CAS ]
[ 1383951-59-4 ]
Yield
Reaction Conditions
Operation in experiment
60%
Dimethyl 4-chloropyridine-2,6-dicarboxylate (6.89 g, 30 mmol) (a), benzene-1,3,5-tris(3',5'-benzenedicarboxylic acid dimethyl ester) (11.53 g, 36 mmol) (b), KI (24.9 g, 150 mmol), K2CO3 (12.4 g, 90 mmol) and CsF (13.67 g, 90 mmol) were dissolved in dried 1,4-dioxane (250 ml), the mixture was purged with argon and stirred for half an hour at room temperature. Then Pd(PPh3)4 (0.4 g, 0.035 mmol) was added and the mixture was heated at 100 C for 10 h. After cooling to room temperature, the precipitate was filtered off, and filtrate was removed under reduced pressure. The residue was purified by silica gel column chromatography with dichloromethane/ethyl acetate 40:1 to give dimethyl 4-(3,5-bis(methoxycarbonyl)phenyl)pyridine-2,6-dicarboxylate as a white solid. A suspension of diester in 1 M NaOH was stirred at 80 C for 2 h. The solution was cooled with ice and acidified with HCl to pH = 2. The white precipitate was collected to give H4dpda in 60% yield based on dimethyl 4-chloropyridine-2,6-dicarboxylate. Anal. calcd for C15H9NO8 (331.23): C, 54.39; H, 2.74; N, 4.23%. Found: C, 54.10; H, 2.84; N, 4.22%.
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 80℃; for 24h;Inert atmosphere;
C (3.3 g, 0.012 mol), bis(pinacolato)diboron (3.4 g, 0.013 mol), dried potassium acetate (3.6 g), [l,r-Bis(diphenylphosphino)ferrocene]palladium(II) dichloride (Pd(dppf)Cl2, 0.2 g, 0.27 mol) were mixed in a 250 mL flask and evacuated for 1 hour before 100 mL dried, degassed l,4-dioxane was added. The reaction was stirred at 80 C under nitrogen atmosphere for 24 hours. After the reaction was completed, organic solvent was removed by rotovap and the remained solid was extracted with dichloromethane. The crude product was purified through a silica plug with a eluent of petroleum ether: ethyl acetate= 8: 1 to give pure D as a white solid (3.5 g, 90 % yield).
72.5%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 100℃; for 12.5h;Inert atmosphere;
5-bromo-1,3-benzenedicarboxylic acid dimethyl ester (5. 4 g, 19.8 mmol), boronic acid pinacol ester (6.0 g, (7.5 g, 57.2 mmol), placed in 250 mL three-necked flask, add anhydrous 1,4-dioxane (50 mL) as solvent, protected by N2, 0 ? 5 h Pd (dppf) 2C12 ( ? 2 g, 0 ? 27 mmol), the temperature was raised to 100 C for 12 h, the temperature dropped to room temperature and the excess of 1,4-dioxane was distilled off. H2O (20 mL ), Extracted with ethyl acetate (30 mL) and extracted three times. The organic phase was collected and dried over anhydrous Na2SO3. The filtrate was evaporated to dryness to give the crude product. The crude product was purified by silica gel column chromatography (eluent: petroleum ether / acetic acid Ethyl ester = 94/6) to afford white powder B (4.59 g) in 72% yield.
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; at 150℃; for 6h;Microwave irradiation; Inert atmosphere;
Figure 15 illustrates synthesis of tetracarboxylate ligand 4 in accordance with one embodiment. The synthesis of (3) shown in Figure 15 includes, in one embodiment, combining 1,4-diiodo-2,3,5,6-tetramethylbenzene (shown as (1) in Figure 15 and can be purchased from VWR) (0.60 g, 1.55 mmol) and 3,5-Bis(methoxycarbonyl) phenylboronic acid pinacol ester (shown as (2) in Figure 15 and prepared following Chen et al., A new multidentate hexacarboxylic acid for the construction of porous metal-organic frameworks of diverse structures and porosities, Cryst. Growth Des. 10, 2775-2779 (2010) (1.09 g, 3.41 mmol), K3PO4(1.97 g, 9.30 mmol) and dioxane (15 ml) in 10-20 ml capacity microwave vials and degassed for 10 min with nitrogen. Pd(PPh3)4(0.040 g, 0.03 mmol) was added and the vial was microwave heated with stirring at 150C for 6 hours. After cooling, CH2CI2(30 mL) was added and the organic layer was washed with water (20 raLchi3). The organic layer was dried over MgS04and evaporated under vacuum. The resulting solid was washed with MeOH and then dried under vacuum to give a white solid (0.S6 g, 70%). NMR (S00 MHz, CDCI3): 5 8.73 (t,J= 1.5Hz 2H), 8.10 (d, J = I.6Hz, 4H), 3.99 (s, 12H), 1.94 (s, 12H); 13C NMR (125MHz, CDCI3) delta 166.4, 143.4, 139.8, 134.8, 132.0, 130.9, 129.1, 52.5, 18.2.
With Pd(OTf)2(CH3CN)4; sodium hydrogencarbonate; N-acetyl-D-tert-leucine; silver carbonate; p-benzoquinone; In tert-Amyl alcohol; water; dimethyl sulfoxide; at 100℃; for 18h;Inert atmosphere;
General procedure: In a 50 ml Schlenk tube, starting material 1 (49.8 mg, 0.2 mmol), 4-methoxycarbonylphenylboronic acid pinacol ester (2) (104.8 mg, 0.4 mmol),Pd(OTf)2(MeCN)4 (11.4 mg, 0.02 mmol), Ac-D-tLeu-OH (3) (6.9 mg, 0.04 mmol),NaHCO3 (100.8 mg, 1.2 mmol), Ag2CO3 (110.3 mg, 0.4 mmol) and 1,4-benzoquinone (10.8 mg, 0.1 mmol) were combined. The flask was evacuated and backfilled with N2 three times, before a solution of dimethylsulfoxide (DMSO,6.0 mg, 0.076 mmol), water (20 mg, 1.1 mmol) and t-amyl-OH (1 ml, 0.2 M) was added. The reaction mixture was then stirred at 100 8C for 18 hours. After being allowed to cool to room temperature, the mixture was diluted with a 1:1 mixture of hexanes:ethyl acetate, and filtered through a pad of celite. The filtrate was concentrated in vacuo, and the resulting residue purified by column chromatography using an eluent of hexanes:ethyl acetate. The product, 1b, was obtained as a light-yellow liquid (62.9 mg, 82%).The above procedure to prepare 1b is generally representative for all the products shown in Tables 3 and 4. Any deviations from this protocol are specified in the footnotes of the tables.
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; at 80℃; for 48h;Inert atmosphere;
Tetramethyl 5,5'-(pyrimidine-2,5-diyl)diisophthalate 2,5-Dibromopyrimidine (1.18 g, 5 mmol), 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) isophthalate (3.52 g, 11 mmol), K3PO4 (2.55 g, 12 mmol) and tetrakis(triphenylphosphine) palladium(0) (0.3 g, 0.26 mmol) were dissolved in dry 1,4-dioxane (80 mL) under N2 atmosphere. The mixture was stirred at 80 C. for two days. After that, the precipitate was collected by filtration, washed with 1,4-dioxane for several times, and then recrystallized in toluene to obtain the pure product. Yield: 56% (1.3 g). 1H NMR (500 MHz, CDCl3, ppm): delta 9.38 (s, 2H), 9.15 (s, 2H), 8.86 (s, 1H), 8.80 (s, 1H), 8.53 (s, 2H), 4.03 (s, 12H).
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane;Inert atmosphere; Reflux;
1,3,5-tris(3',5'-dicarboxybiphenyl-4-yl)benzene 1,3,5-Tris(4-bromophenyl)benzene (0.980 g, 1.81 mmol), dimethyl isophthalate-5-pinacolboronate (2.08 g, 6.50 mmol), K3PO4 (tribasic, 3.84 g, 18.1 mmol) and 1,4-dioxane (100 mL) are added into a 200 mL round-bottomed flask equipped with a magnetic stirrer and water jacketed condenser. The resulting suspension is degassed for 15 min. by sparging with nitrogen gas. Pd(PPh3)4 (0.157 g, 0.136 mmol) is added, and the mixture is heated to reflux overnight under a nitrogen atmosphere. After cooling to room temperature, the reaction mixture is poured in H2O (100 mL) and the precipitate is collected by filtration and washed with a minimal amount of THF. The crude material is dissolved in dioxane/H2O (10:1, 110 mL), KOH (1.72 g, 30.6 mmol) is added and the mixture is heated to reflux for 12 hours. The solvent is removed by evaporation and the residue is dissolved in H2O (100 mL). The residual solids are filtered off and the filtrate is acidified with concentrated HCl (20 mL). The target compound is collected by filtration, washed with H2O and acetone and dried under vacuum to yield 0.783 g of 1 (0.980 mmol as a white powder, 54%): mp>300 C.; 1H NMR (400 MHz, DMSO-d6): delta 13.39 (s, 6H), 8.43 (s, 3H), 8.42 (s, 6H), 8.04 (d, 3J=8.2 Hz, 6H), 8.02 (s, 3H), 7.86 (d, 3J=8.2 Hz, 6H) ppm; 13C NMR (100 MHz, DMSO-d6): delta 166.9, 141.4, 140.9, 140.3, 138.1, 132.5, 131.6, 129.3, 128.4, 127.8, 124.9 ppm; HRMS (EI) calcd. for C48H30O12 (m/e): 798.1737. found: 798.1751.
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