* 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.
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate In toluene at 90 - 100℃; for 6 h; Sealed tube
Pd(dppf)Cl2.CH2Cl2 (0.48 g, 0.0005 mole) was added to a sealed tube containing a mixture of 4-bromobenzaldehyde (1 g, 0.005 mole), potassium acetate (1.31 g, 0.013 mole) and bis(pinacolato)diboron (1.6 g, 0.006 mole) in toluene (20 mL) and the contents were heated at 90 - 100 °C for 6 hours and then cooled to room temperature. The reaction mass filtered through a pad of celite and washed with ethyl acetate (20 mL x 2). The filtrate was concentrated under vacuum to obtain the crude compound that was further purified by flash chromatography using ethyl acetate:hexanes (10:90) to obtain 4-(4,4,5,5- tetramethyl-[l,3,2]dioxaborolan-2-yl)benzaldehyde. Yield: 1.12 g; l - NMR (CDC13, 400 MHz) δ ppm: 1.36 (s, 12H), 7.85 - 7.87 (d, J = 7.72 Hz, 2H), 7.95 - 7.97 (d, J = 7.8 Hz, 2H), 10.05 (s, 1H); Mass (m/z): 233.0 (M+H)+.
Reference：
[1] Advanced Synthesis and Catalysis, 2016, vol. 358, # 6, p. 977 - 983
[2] Patent: WO2013/170165, 2013, A1, . Location in patent: Page/Page column 93
[3] Applied Organometallic Chemistry, 2011, vol. 25, # 7, p. 537 - 541
[4] Organic Letters, 2016, vol. 18, # 20, p. 5248 - 5251
[5] Journal of the American Chemical Society, 2016, vol. 138, # 1, p. 84 - 87
[6] Synthetic Communications, 2007, vol. 37, # 5, p. 667 - 674
[7] Journal of Materials Chemistry, 2011, vol. 21, # 14, p. 5451 - 5456
[8] Angewandte Chemie - International Edition, 2012, vol. 51, # 2, p. 536 - 539
[9] Patent: WO2018/42362, 2018, A1, . Location in patent: Page/Page column 51
[10] Patent: WO2018/195321, 2018, A1, . Location in patent: Page/Page column 493; 494
2
[ 76-09-5 ]
[ 87199-17-5 ]
[ 128376-64-7 ]
Yield
Reaction Conditions
Operation in experiment
91%
at 20℃; for 2 h;
To a solution of 4-formylphenylboronic acid (1 g) in anhydrous THF (10 ml_) was added 2,3-dimethyl-butane-2,3-diol (0.867 mg) and the mixture was EPO <DP n="15"/>stirred at room temperature for 2 hours. The solvent was evaporated to dryness. The residue was dissolved in dichloromethane (40 ml_), washed with water (25 ml_ x 3), dried and evaporated under vacuum to obtain 4-(4,4,5,5- tetramethyl-[1 ,3,2]dioxaborolan-2-yl)-benzaldehyde (1.41 g, 91percent yield). 1H- NMR (400 MHz, CDCI3): δ 1.34 (s, 12 H, 4 CH3), 7.86 (d, J = 8.4 Hz, 2 H, H- Ar), 7.96 (d, J = 8 Hz, 2 H, H-Ar), 10.05 (s, 1 H, CHO) ppm.
91%
at 20℃; for 2 h;
Example 2: Preparation of 4-(4A5,5-tetramethyl-H ,3,21dioxaborolan-2-yl)- benzaldehvde; To a solution of 4-formylphenylboronic acid (1 g) in anhydrous THF (10 mL) was added 2,3-dimethyl-butane-2,3-diol (0.867 mg) and the mixture was stirred at room temperature for 2 hours. The solvent was evaporated to dryness. The residue was dissolved in dichloromethane (40 mL), washed with water (25 mL x 3), dried and evaporated under vacuum to obtain 4-(4, 4,5,5- tetramethyl-[1 ,3,2]dioxaborolan-2-yl)-benzaldehyde (1.41 g, 91 percent yield). 1H- NMR (400 MHz, CDCI3): δ 1.34 (s, 12 H, 4 CH3), 7.86 (d, J = 8.4 Hz, 2 H, H- Ar), 7.96 (d, J = 8 Hz, 2 H, H-Ar), 10.05 (s, 1 H, CHO) ppm.
Reference：
[1] Synthetic Communications, 2002, vol. 32, # 17, p. 2669 - 2676
[2] European Journal of Organic Chemistry, 2000, # 9, p. 1703 - 1710
[3] Israel Journal of Chemistry, 2009, vol. 49, # 1, p. 1 - 8
[4] Journal of Organic Chemistry, 2007, vol. 72, # 12, p. 4328 - 4339
[5] Journal of Physical Chemistry A, 2017, vol. 121, # 40, p. 7550 - 7564
[6] Journal of the American Chemical Society, 2003, vol. 125, # 32, p. 9668 - 9681
[7] Journal of the American Chemical Society, 2003, vol. 125, # 32, p. 9668 - 9681
[8] Applied Organometallic Chemistry, 2019, vol. 33, # 1,
[9] Organic Letters, 2003, vol. 5, # 23, p. 4389 - 4392
[10] Patent: WO2006/67216, 2006, A2, . Location in patent: Page/Page column 13-14
[11] Patent: WO2007/71750, 2007, A1, . Location in patent: Page/Page column 17
[12] Tetrahedron, 2001, vol. 57, # 45, p. 9285 - 9298
[13] Organic Letters, 2010, vol. 12, # 14, p. 3216 - 3218
[14] Journal of Materials Chemistry B, 2018, vol. 6, # 16, p. 2489 - 2496
[15] Chem, 2017, vol. 3, # 3, p. 437 - 460
[16] Canadian Journal of Chemistry, 2001, vol. 79, # 7, p. 1115 - 1123
[17] Canadian Journal of Chemistry, 2001, vol. 79, # 7, p. 1115 - 1123
[18] Journal of the American Chemical Society, 2010, vol. 132, # 21, p. 7268 - 7269
[19] Acta Crystallographica Section C: Crystal Structure Communications, 2012, vol. 68, # 6, p. o213-o215
[20] Journal of the American Chemical Society, 2013, vol. 135, # 7, p. 2552 - 2559
[21] Organic Letters, 2013, vol. 15, # 18, p. 4850 - 4853
[22] Molecules, 2013, vol. 18, # 10, p. 12346 - 12367
[23] Journal of Organic Chemistry, 2015, vol. 80, # 6, p. 3036 - 3049
[24] Organic Letters, 2015, vol. 17, # 12, p. 3086 - 3089
[25] Arkivoc, 2016, vol. 2017, # 2, p. 107 - 117
[26] Journal of Organic Chemistry, 2018, vol. 83, # 4, p. 1842 - 1851
[27] Inorganic Chemistry, 2018, vol. 57, # 9, p. 4877 - 4890
[28] Patent: US6576789, 2003, B1,
3
[ 104-88-1 ]
[ 73183-34-3 ]
[ 128376-64-7 ]
Reference：
[1] Journal of Organic Chemistry, 2012, vol. 77, # 7, p. 3543 - 3548
[2] RSC Advances, 2018, vol. 8, # 25, p. 13643 - 13648
[3] Organic Letters, 2002, vol. 4, # 4, p. 541 - 543
[4] Tetrahedron, 2001, vol. 57, # 49, p. 9813 - 9816
4
[ 195062-57-8 ]
[ 128376-64-7 ]
Yield
Reaction Conditions
Operation in experiment
84%
With N-Bromosuccinimide; dibenzoyl peroxide In 1,4-dioxane; water for 12 h; Inert atmosphere; Reflux
Operation is the same as in Example 1, and the feed is as follows:21.8 g (0.1 mol) of p-methylphenylboronic acid pinacol ester, 39.2 g (0.22 mol) of N-bromosuccinimide,150 ml of dioxane and 0.5 g (0.002 mol) of benzoyl peroxide.The obtained product was 19.5 g of p-formylphenylboronic acid pinacol ester with a yield of 84percent. The analysis data is shown in Example 1. In a 500 ml three-necked flask with mechanical stirring, a nitrogen inlet and a reflux condenser, 21.8 g (0.1 mol) p-methylphenylboronic acid pinacol ester were successively added.35.6 g (0.2 mol) of N-bromosuccinimide, 150 ml of dioxane and 0.24 g (0.001 mol) of benzoyl peroxide, and then heated to reflux under nitrogen protection until the sterol esters of p-methylphenylboronic acid disappeared. Then 150 ml of water was added and the mixture was heated and refluxed for 12 hours.Into a distillation apparatus, most of the solvent was distilled off, the residue was cooled to room temperature, extracted with dichloromethane, and dried over anhydrous sodium sulfate.Filtration, adding petroleum ether to cloud point, standing at low temperature (0-5°C), filtering and precipitating the product, yielding 16.5 g of p-formylphenylboronic acid pinacol ester in a yield of 71percent.
Reference：
[1] Patent: CN107903280, 2018, A, . Location in patent: Paragraph 0040-0064
With potassium carbonate In tolueneInert atmosphere; Reflux
4'-trifiuoromethy.biphenyi-4-carbaldehyde (Compound 25}Pd(PPh3)4 (6 g) was added to a mixture of 4-fbrmyiphenylboronic acid plnacoS cyclic ester (53 g, 0,22 mol), 4-trifluoromethylbromobenzene(50 g, 0.22 mol), and potassium carbonate (63 g, 0.46 mol) In toluene (2 L) under nitrogen protection. The mixture was refiuxed overnight. After cooling to room temperature, the solvent was removed under vacuum. To the residue were added water (l L) and ethyl acetate (1 L), The organic phase was collected, and the water phase was extracted with ethyl acetate (1 L x2). The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated. The crude product was purified by HPFC (PE: EA = 50: 1) to afford the title compound (50.2 g, 90.1percent). LC- S: 251.2 (M+l).
Reference：
[1] Journal of the American Chemical Society, 2016, vol. 138, # 1, p. 84 - 87
22
[ 6852-58-0 ]
[ 73183-34-3 ]
[ 25015-63-8 ]
[ 128376-64-7 ]
[ 380151-85-9 ]
[ 380151-86-0 ]
Reference：
[1] Journal of the American Chemical Society, 2016, vol. 138, # 1, p. 84 - 87
23
[ 128376-64-7 ]
[ 302348-51-2 ]
Yield
Reaction Conditions
Operation in experiment
513 mg
at 20℃; for 5 h;
To a mixture of a4-formylbenzenboronic acid (1a, 375 mg, 2.50 mmol), pinacol (355 mg, 3.00 mmol) and anhydrous magnesium sulfate (625 mg, 5.00 mmol), methanol was added (12.50 mL). The mixture was stirred at room temperature for 6 h. After the reaction was completed, the crude solution was filtered, and then sodium borohydride (47 mg, 1.25 mmol) was added to the filtrate. Afterwards, the reaction mixture was stirred for an additional 5 h. Once the reaction was completed, the reaction mixture was filtered and the filtrate was concentrated in vacuo to give the desired product 2a as a white solid (m.p. 75–77 °C) in88percent yield (513 mg). 1H-NMR (CD3OD-d4) δ ppm 7.71 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 7.8 Hz, 2H),4.62 (s, 2H), 1.34 (s, 12H); 13C-NMR (CD3OD-d4) δ ppm 146.23, 135.93, 127.26, 85.19, 65.24, 25.34;11B-NMR (CDCl3) δ ppm 34.82.
Reference：
[1] Synthetic Communications, 2002, vol. 32, # 17, p. 2669 - 2676
[2] Bioorganic and Medicinal Chemistry Letters, 2009, vol. 19, # 9, p. 2487 - 2491
[3] Israel Journal of Chemistry, 2009, vol. 49, # 1, p. 1 - 8
[4] Molecules, 2013, vol. 18, # 10, p. 12346 - 12367
24
[ 128376-64-7 ]
[ 454185-98-9 ]
Reference：
[1] Journal of Organic Chemistry, 2016, vol. 81, # 19, p. 8673 - 8695
25
[ 128376-64-7 ]
[ 439090-73-0 ]
Reference：
[1] Canadian Journal of Chemistry, 2002, vol. 80, # 1, p. 31 - 40
26
[ 95-55-6 ]
[ 128376-64-7 ]
[ 439090-73-0 ]
Reference：
[1] Canadian Journal of Chemistry, 2002, vol. 80, # 1, p. 31 - 40
27
[ 90965-06-3 ]
[ 128376-64-7 ]
[ 1034287-04-1 ]
Reference：
[1] Synlett, 2007, # 19, p. 3037 - 3041
28
[ 591-17-3 ]
[ 128376-64-7 ]
[ 400744-83-4 ]
Reference：
[1] Green Chemistry, 2012, vol. 14, # 3, p. 661 - 667
In diethyl ether at 25℃; for 24h; Inert atmosphere; Schlenk technique;
91%
In diethyl ether at 20℃;
91%
In tetrahydrofuran at 20℃; for 2h;
3
To a solution of 4-formylphenylboronic acid (1 g) in anhydrous THF (10 ml_) was added 2,3-dimethyl-butane-2,3-diol (0.867 mg) and the mixture was EPO stirred at room temperature for 2 hours. The solvent was evaporated to dryness. The residue was dissolved in dichloromethane (40 ml_), washed with water (25 ml_ x 3), dried and evaporated under vacuum to obtain 4-(4,4,5,5- tetramethyl-[1 ,3,2]dioxaborolan-2-yl)-benzaldehyde (1.41 g, 91% yield). 1H- NMR (400 MHz, CDCI3): δ 1.34 (s, 12 H, 4 CH3), 7.86 (d, J = 8.4 Hz, 2 H, H- Ar), 7.96 (d, J = 8 Hz, 2 H, H-Ar), 10.05 (s, 1 H, CHO) ppm.
91%
In tetrahydrofuran at 20℃; for 2h;
2
Example 2: Preparation of 4-(4A5,5-tetramethyl-H ,3,21dioxaborolan-2-yl)- benzaldehvde; To a solution of 4-formylphenylboronic acid (1 g) in anhydrous THF (10 mL) was added 2,3-dimethyl-butane-2,3-diol (0.867 mg) and the mixture was stirred at room temperature for 2 hours. The solvent was evaporated to dryness. The residue was dissolved in dichloromethane (40 mL), washed with water (25 mL x 3), dried and evaporated under vacuum to obtain 4-(4, 4,5,5- tetramethyl-[1 ,3,2]dioxaborolan-2-yl)-benzaldehyde (1.41 g, 91 % yield). 1H- NMR (400 MHz, CDCI3): δ 1.34 (s, 12 H, 4 CH3), 7.86 (d, J = 8.4 Hz, 2 H, H- Ar), 7.96 (d, J = 8 Hz, 2 H, H-Ar), 10.05 (s, 1 H, CHO) ppm.
90%
In diethyl ether at 20℃; for 15h;
86%
In benzene for 1h; Inert atmosphere; Reflux;
85%
In toluene at 113℃; for 8h; Inert atmosphere;
81.9%
In tetrahydrofuran; toluene
2. Synthesis of 4-(tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde(i)
4-Formyl-phenyl boronic acid (149 mg, 1 mmol) and pinacol (118 mg, 1 mmol) were added to THF (10 mL) and Toluene (10 mL). The mixture was concentrated to dryness under reduced pressure and this procedure (solvents addition/evaporation) was repeated three times. (81.9% yield).
71%
With 4 A molecular sieve In dichloromethane for 120h;
71%
In dichloromethane boronic acid reacted with 1 equiv. of pinacol in CH2Cl2 in the presence of activated molecular sieves (type 4A) for 5 days; sieves removed by suction filtration; solvent removed under vacuum; elem. anal.;
at 20℃; for 1h;
Schnuerch, M., Holzweber, M., Mihovilovic, M.D., Stanetty, P. (2007), Green Chem. 9, 139-145;
In diethyl ether at 20℃; Inert atmosphere; Molecular sieve;
In toluene for 2h; Dean-Stark; Inert atmosphere; Reflux;
With magnesium sulfate In methanol at 20℃; for 6h;
To a mixture of a4-formylbenzenboronic acid (1a, 375 mg, 2.50 mmol), pinacol (355 mg, 3.00 mmol) and anhydrous magnesium sulfate (625 mg, 5.00 mmol), methanol was added (12.50 mL). The mixture was stirred at room temperature for 6 h. After the reaction was completed, the crude solution was filtered, and then sodium borohydride (47 mg, 1.25 mmol) was added to the filtrate. Afterwards, the reaction mixture was stirred for an additional 5 h. Once the reaction was completed, the reaction mixture was filtered and the filtrate was concentrated in vacuo to give the desired product 2a as a white solid (m.p. 75-77 °C) in88% yield (513 mg). 1H-NMR (CD3OD-d4) δ ppm 7.71 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 7.8 Hz, 2H),4.62 (s, 2H), 1.34 (s, 12H); 13C-NMR (CD3OD-d4) δ ppm 146.23, 135.93, 127.26, 85.19, 65.24, 25.34;11B-NMR (CDCl3) δ ppm 34.82.
2.3 g
In toluene at 120℃; for 12h; Inert atmosphere;
In diethyl ether at 20℃; Molecular sieve;
In acetone at 20℃; for 2h;
4-formylboronic acid (1.1 g, 7.3mmol) and pinacol (0.9 g, 7.3 mmol) were dissolved in acetone (40 mL) and left at room temperature for 2 h.Evaporation of the solvent produced light beige solid. It was dissolved in toluene (40 mL) and benzylamine(0.84 mL, 7.7 mmole) was added and the mixture was refluxed for 1.5 h for azeotropic removal of formedwater. To the obtained solution diethyl phosphite (0.97 mL, 7.6 mmole) was then added and refluxingcontinued for 3h. After evaporation of solvent crude oil was chromatographically purified using hexane/ CHCl3gradient (from 95% to 85% of hexane) as eluent yielding yellow solidifying oil (1.74 g, 52%).
In ethyl acetate at 40℃;
In toluene at 120℃; for 12h; Inert atmosphere;
In toluene
5 4-(4,4,5,5-Tetramethyl[1,3,2]dioxaborolan-2-yl)benzaldehyde
Example 5 4-(4,4,5,5-Tetramethyl[1,3,2]dioxaborolan-2-yl)benzaldehyde A suspension of 5 g (33.3 mmol) of 4-formylphenylboronic acid and 3.93 g (33.3 mmol) of pinacol in 25 ml of toluene was refluxed on a water separator. When all the water of reaction had been removed, a clarifying filtration was carried out, and the solvent was removed by distillation until the product started to crystallize, giving 7.2 g (31 mmol) of product.
In diethyl ether at 20℃; for 18h; Inert atmosphere;
In diethyl ether
In toluene at 80℃; for 8h;
1.2-5.2
(2) Weigh 1.5 g of 4-formylphenylboronic acid and 1.18 g of pinacol in a 500 ml flask, and add 150 ml of toluene. The mixture was reacted for 8 hours under heating at reflux at 80°C. After the reaction was completed, the solvent toluene was removed under reduced pressure distillation conditions, and white 4-formylphenylboronic acid pinacol ester was precipitated, and the product was directly used in the next reaction.
In toluene at 80℃; for 8h;
1.2; 2.2; 3.2; 4.2; 5.2
Weigh 1.5 g of 4-formylphenylboronic acid and 1.18 g of pinacol into a 500 ml flask, and add 150 ml of toluene. The mixture was reacted for 8 hours under heating and refluxing conditions at 80°C.After the reaction was completed, the solvent toluene was removed under reduced pressure distillation conditions, and white 4-formylphenylboronic acid pinacol ester was precipitated, and the product was directly used in the next reaction.
In toluene at 120℃; for 12h;
1.2; 2.2; 3.2; 4.2; 5.2; 6.2
(2) Weigh 1.5 g of 4-formylphenylboronic acid and 1.18 g of pinacol in a 500 ml flask, and add 150 ml of toluene. The mixture was reacted for 12 hours under heating and refluxing conditions at 120°C. After the reaction is completed, the solvent toluene is removed under reduced pressure distillation conditions, and white 4-formylphenylboronic acid pinacol ester is precipitated, and the product is directly used in the next reaction
To a mixture of a4-formylbenzenboronic acid (1a, 375 mg, 2.50 mmol), pinacol (355 mg, 3.00 mmol) and anhydrous magnesium sulfate (625 mg, 5.00 mmol), methanol was added (12.50 mL). The mixture was stirred at room temperature for 6 h. After the reaction was completed, the crude solution was filtered, and then sodium borohydride (47 mg, 1.25 mmol) was added to the filtrate. Afterwards, the reaction mixture was stirred for an additional 5 h. Once the reaction was completed, the reaction mixture was filtered and the filtrate was concentrated in vacuo to give the desired product 2a as a white solid (m.p. 75?77 °C) in88percent yield (513 mg). 1H-NMR (CD3OD-d4) delta ppm 7.71 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 7.8 Hz, 2H),4.62 (s, 2H), 1.34 (s, 12H); 13C-NMR (CD3OD-d4) delta ppm 146.23, 135.93, 127.26, 85.19, 65.24, 25.34;11B-NMR (CDCl3) delta ppm 34.82.
With potassium carbonate In toluene at 20℃; Inert atmosphere; Reflux;
1
4'-fluoroblpheny{-4-carbaldehyde (Compound 20)Pd(PPh3)4 (3 g) was added to a mixture of 4-formylphenylboronic acid pinacol cyclic ester (26.5 g, 0.11 moi), 4-bromofiuorobenzene(20 g, 0.1.1 moi), and potassium carbonate (31.5 g, 0.23 moi) in toluene (1 L) under nitrogen protection. The mixture was refluxed overnight. After cooling to room temperature, the solvent was removed under vacuum. To the residue were added water (500 ml) and ethyl acetate (500 ml). The organic phase was collected, and the water phase was extracted with ethyl acetate (500 ml x2). The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated. The crude product was purified by HPFC (PE: EA «= 50: 1) to afford 4'-fiuorobiphenyl-4-carbaldehyde (19.3 g, 87,7%). LC-MS: 201.2 ( +l).
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In toluene;Inert atmosphere; Reflux;
4'-trifiuoromethy.biphenyi-4-carbaldehyde (Compound 25}Pd(PPh3)4 (6 g) was added to a mixture of 4-fbrmyiphenylboronic acid plnacoS cyclic ester (53 g, 0,22 mol), 4-trifluoromethylbromobenzene(50 g, 0.22 mol), and potassium carbonate (63 g, 0.46 mol) In toluene (2 L) under nitrogen protection. The mixture was refiuxed overnight. After cooling to room temperature, the solvent was removed under vacuum. To the residue were added water (l L) and ethyl acetate (1 L), The organic phase was collected, and the water phase was extracted with ethyl acetate (1 L x2). The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated. The crude product was purified by HPFC (PE: EA = 50: 1) to afford the title compound (50.2 g, 90.1%). LC- S: 251.2 (M+l).
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In 1,4-dioxane; methanol; at 80℃; for 15.0h;Inert atmosphere;
To a stirring solution of compound 2.3 (32.4 g,. 0.14 mol). compound 2,4 (32.2 g, 0.17 mol) and Pd(PPh2)4 (8.08 g, 7 ram of) in 1 ,4-dioxane/nrietrianoi (800 rnL 1 :1) was added Na2COs (22.3 g,u.21 mol) under an argon atmosphere and the mixture was stirred at 80C for 15 nr. The solvent was removed under reduced pressure and the resulting residue was diluted with wafer (500 rnL) and extracted with EtOAc (3 x 500 ml). The combined organic layers were dried and concentrated under reduced pressure to give a crude, which was purified by flash chromatography (silica gel/ RhoEpsilon.Alpha 2: 1) to give ethyl 4-(4-formylphenyl picolinate (2.5, 14.2 g, 40%) as a yellow solid.
(Z)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-4'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)stilbene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With sodium t-butanolate In N,N-dimethyl-formamide at 20℃; Inert atmosphere; Overall yield = 90%; Overall yield = 0.084 g;
.1.7 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan)-4/-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)stilbene (1e)
4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde (0.05g, 0.21mmol) was added to a solution of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaboratophenyl)-methyl triphenylphosphonium bromide (4) (0.120g, 0.21mmol) in anhydrous DMF (7mL) under nitrogen atmosphere. Sodium tert-butanolate (0.062g, 0.64mmol) was added to the clear solution at room temperature, and the mixture was stirred for 4h. The reaction mixture was poured into water (20mL) and neutralized with 1M HCl. Then the resulting mixture was extracted by EtOAc (3×10mL), washed with H2O and brine, dried over anhydrous Na2SO4 and filtered. Evaporation of the solvent followed by column chromatography on silica gel to obtain the pure product 1e as a mixture of E/Z. Yield: 0.084g (90%). 1H NMR (300MHz, CDCl3): δ 1.36 (s), 1.37 (s), 7.20 (s), 7.21-7.7.29 (m), 7.53-7.56 (d, J=9Hz), 7.64-7.68 (m), 7.81-7.84 (d, J=9Hz). 13C NMR (75MHz, CDCl3): δ 25.3, 84.5, 125.8, 128.3, 129.8, 135.2, 140.0. HRMS (ESI): m/z calcd. for C26H34B2O4 [M+Na]+ 455.2541, found 455.2555.
4-(benzo[c][1,2,5]thiadiazol-4-yl)benzaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 12h;Inert atmosphere; Reflux;
In a first step, 10 g (73.52 mmol) of 2,1,3-benzothiadiazole (1) was added to a 100 ml round-Suspended in 50 ml HBr solution (48percent),A solution of 2.8 ml (54.26 mmol) of bromine was added dropwise with vigorous stirring,After all the drops were added, the mixture was heated to 150 ° C and refluxed for 2 hours.After completion of the reaction, the mixture was cooled to room temperature,The reaction mixture was poured into 500 ml of water,The precipitated solid was filtered to give 10.4 g of crude product;The crude product contains a small amount of dibromo substituted product as well as the starting material.The crude product is directly put into the next step.Under nitrogen protection,To a 500 ml two-necked round bottom flask equipped with a condenser tube was added 8.556 g of crude product (assuming all <strong>[22034-13-5]4-bromo-2,1,3-benzothiadiazole</strong> (2), 40 mmol)10.208 g (44 mmol) of 4-formylphenylboronic acid pinacol ester,2.32 g (2.0 mmol) of tetrakis (triphenylphosphine) palladium and 200 ml of THF,Followed by the addition of 200 ml of an aqueous solution of potassium carbonate (11.06 g, 80 mmol), heated to reflux and stirred for 12 h.After completion of the reaction, the mixture was cooled to room temperature and the mixture was extracted three times with dichloromethane. The separated organic layer was dried over anhydrous sodium sulfate. The crude product obtained by distilling off the solvent under reduced pressure was treated with dichloromethane / petroleum ether (2: 1) as the eluent,Silica gel column chromatography afforded 8.2 g of pale yellow 4-formylphenyl-2,1,3-benzothiadiazole (3).
tert-butyl N-({4-[([4-(tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]methyl}amino)methyl]phenyl}methyl)carbamate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
73%
With sodium tris(acetoxy)borohydride; In dichloromethane; at 20℃;Inert atmosphere;
Boc protected p-xylylenediamine (ii) (142 mg, 0.6 mmol) and pinacol (i) (139 mg, 0.6mmol) protected boronic acid were added into 18 mL DCM, 178 mg (0.6 mmol) Sodium triacetoxyborohydride was subsequently added. The mixture was stirred overnight at room temperature under nitrogen. MilliQ water was added to quench sodium triacetoxyborohydride and tert-butyl N-({4-[([4-(tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]methyl}amino)methyl]phenyl}methyl) carbamate was extracted in DCM and washed by water. DCM was evaporated to yield 202 mg of white solid (73% yield).
4,4'-(3-hexylthiophene-2,5-diyl)dibenzaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
86%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; tetrabutylammomium bromide; sodium carbonate; In water; at 80℃; for 0.25h;Inert atmosphere; Microwave irradiation;
Deionized water (3 mL) was added to a mixture of boronic ester 11 (0.58 g, 2.5 mmol), dibromo-3-hexylthiophene (0.33 g, 1.0 mmol), t-butylammonium bromide (0.64 g, 2.0 mmol) and sodium carbonate (0.40 g, 3.8 mmol) in a microwave (MW) vessel under nitrogen atmosphere. After bubbling nitrogen through the mixture for 3 minutes, [PdCl2(dppf)] (0.08 g, 0.1 mmole) was added to the reaction mixture and the vessel was then placed inside a CEM Discover S-Class microwave synthesizer. The reaction was exposed to microwaves at 80 C. (100 W) for 15 minutes and then diluted with ethyl acetate (20 mL) at room temperature followed by filtration through a pad of celite. The organic layer was washed with brine (5 mL), dried over Na2SO4 and evaporated under reduced pressure. The residues were resolved over silica column, eluting with ethyl acetate-hexane (15:85) to get the title compound 12 as a light yellow solid (0.35 g, 86%). 1H-NMR (500 MHz, CDCl3): delta 0.89 (t, J=7.0 Hz, 3H, CH3), 1.29-138 (m, 8 H, Aliphatic-H), 1.69 (m, 2H, Aliphatic-H), 2.73 (t, J=6.7 Hz, 2H, CH2), 7.41 (s, 1H, Ar-H), 7.66 (d, J=7.6 Hz, 2H, Ar-H), 7.78 (d, J=7.5 Hz, 2H, Ar-H), 7.92 (d, J=8.2 Hz, 2H, Ar-H), 7.97 (d, J=8.1 Hz, 2H, Ar-H), 10.03 (s, 1H, CHO), 10.08 (s, 1H, CHO).
4-(6-(trifluoromethyl)pyridin-3-yl)benzaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
79.7%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,4-dioxane; water; at 100℃; for 6h;
4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)benzaldehyde 2a(2.32g, 10.0mmol),<strong>[436799-32-5]5-bromo-2-(trifluoromethyl)pyridine</strong> 2b (2.94 g, 13.0 mmol),Tetratriphenylphosphine palladium (578 mg, 0.50 mmol) and sodium carbonate (3.18 g, 30.0 mmol)Soluble in a mixed solution of 34 mL 1,4-dioxane and water (V/V/V=9/1)The reaction was carried out at 100 C for 6 hours under nitrogen protection.The reaction solution was cooled to room temperature and concentrated under reduced pressure.The resulting residue was purified by silica gel column chromatography (eluent: System A).4-(6-(trifluoromethyl)pyridin-3-yl)benzaldehyde 2c (2.00 g, pale yellow solid) was obtained, yield: 79.7%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,2-dimethoxyethane; water; at 90℃; for 5h;Inert atmosphere;
4-(4,4,5,5-tetramethyl-1,3,2-dioxaborol-2-yl)benzaldehyde 2a (2.32 g, 10.0 mmol),<strong>[50488-42-1]2-bromo-5-(trifluoromethyl)pyridine</strong> 3a (2.05 g, 9.10 mmol),Tetratriphenylphosphine palladium (526 mg, 0.445 mmol) and sodium carbonate (2.40 g, 22.6 mmol)Soluble in a mixed solution of 25 mL ethylene glycol dimethyl ether and water (V/V=4/1)The reaction was carried out at 90 C for 5 hours under nitrogen protection. The reaction solution was cooled to room temperature and concentrated under reduced pressure.The resulting residue was purified by silica gel column chromatography (eluent: System A).4-(5-(trifluoromethyl)pyridin-2-yl)benzaldehyde 3b (1.58 g, white solid) was obtained in a yield of 69.3%.
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate; In 1,4-dioxane; water; at 80℃; for 6h;
Pd(dppf)Cl2.CH2Cl2 (0.17 g, 0.0002 mole) was added to a stirred mixture of 4- bromothiazole (0.7 g, 0.004 mol), sodium carbonate ( 1.3 g, 0.012 mole) and 4-(4,4,5,5- tetramethyl-[l,3,2]dioxaborolan-2-yl)benzaldehyde (1.89 g, 0.008 mole) in a mixture of 1,4-dioxane and water (25 mL, 4: 1). The reaction mixture was heated to 80 °C and maintained for 6 hours, cooled to RT, diluted with H20 (10 mL), extracted with ethyl acetate (25 mL x 3). The organic extracts were combined, dried over anhydrous Na2S04 and concentrated under vacuum to obtain the crude 4-(thiazol-4-yl) benzaldehyde that was used as such for further reaction.
With piperidine In N,N-dimethyl-formamide at 130℃; for 0.166667h; Microwave irradiation;
1 1.General synthesis methods of compound 1-10
General procedure: 0.1 millimolar (or 0.2 millimolar) of the corresponding BODIPY and 0.35 equivalents of aromatic aldehyde were added to a microwave tube, the substrate was dissolved with 2 ML (or 4 ML) of dry DMF, then the catalyst: 50 [mu]L (or 100 [mu]L) of piperidine and 50 [mu]L (Or 100 μL) acetic acid was added to the reaction mixture. Using a Biotage microwave reactor, 10-45 Min was reacted at 130°C.Then use an oil pump as a vacuum source and evaporate off the solvent. Finally, the target compound is purified by column chromatography or thin layer chromatography.
N-(2-(tert-butylamino)-2-oxo-1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)ethyl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
88%
General procedure: N-(2-(tert-Butylamino)-2-oxo-1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)ethyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzamide (1) A 10-mL glass tube containing 4-aminophenylboronic acid pinacol ester (300 mg, 1.37 mmol), 4-formylphenylboronic acid pinacol ester (256 mg, 1.09 mmol), and 2.7 mL methanol was first stirred for 60 min under microwave irradiation (50 C, 150 W). Then, 4-carboxyphenylboronic acid pinacol ester (374 mg, 1.51 mmol) and tert-butyl isocyanide (0.2 mL, 1.37 mmol) were added to the reaction mixture. Microwave irradiation was applied again for an additional 120 min (50 C, 150 W) under medium-speed magnetic stirring, and the reaction mixture was concentrated and redissolved in ethylacetate. The crude solution was then washed with 1 M HCl(aq) and NaHCO3(aq), respectively. The organic solution was collected and dried over MgSO4 and concentratedin vacuo. The resulting crude material was purified by flash chromatography with ethyl acetate:n-hexane = 3:7 to afford the desired product in 85 %yield (708.19 mg).
Stage #1: 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde With ammonia; hydrogen In <i>tert</i>-butyl alcohol at 120℃; for 24h; Autoclave; High pressure;
Stage #2: With hydrogenchloride at 20℃;
3,4-(methylenedioxy)-α-tolueneisonitrile[ No CAS ]
[ 128376-64-7 ]
[ 611-01-8 ]
2-((benzo[d][1,3]dioxol-5-ylmethyl)amino)-2-oxo-1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)ethyl2,4-dimethylbenzoate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
87%
With potassium carbonate; In methanol; at 20℃; for 24h;Green chemistry;
General procedure: the corresponding aldehyde (1 mmol), acid (1 mmol), and isocyanide (1 mmol) were added to a 5-mL flask along with 3 mL of methanol as a solvent. The reaction mixture was stirred for24 h at room temperature. The crude mixture was evaporated and subjected to column chromatography(petroleum ether/ethyl acetate) affording the title compounds.
4-methyl-3-oxo-2-(2-oxo-1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)ethyl)-N-phenylpentanamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
14%
With 3-ethyl-5-(2-hydroxyethyl)-4-methyl-1,3-thiazolium bromide; triethylamine; In neat (no solvent); at 75℃;Inert atmosphere;
A mixture of <strong>[125971-57-5]2-benzylidene-4-methyl-3-oxo-N-phenylpentanamide</strong> (1, 5 g, 17 mmol, 1.00equiv.), 3-ethyl-5-(2-hydroxyethyl)-4-methyl-3-thiazolium bromide (3, 1.7 g, 6.8 mmol, 0.40 equiv.),triethylamine (5 mL, 36 mmol, 2.12 equiv.), and 4-formylphenylboronic acid pinacol ester (2, 4.9 g,21 mmol, 1.20 equiv.) was heated at 75 C under argon atmosphere with vigorous stirring for16 h. The reaction was monitored by thin-layer chromatography (TLC) until the consumption ofthe N-phenylpentanamide (1). Isopropyl alcohol (25 mL) was added, and the reaction mixturewas maintained at 25 C for 4 h under stirring. The remaining solid was vacuum filtered andwashed with 25 mL of water followed by 20 mL of isopropyl alcohol. The product was driedunder high vacuum for 4 h, aording 4-methyl-3-oxo-2-(2-oxo-1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)ethyl)-N-phenylpentanamide (4) as a yellowish crystalline solid inapproximately 14% yield (1.8 g, 2.4 mmol).
N-(5-(4-formylphenyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)cyclopropanecarboxamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
75%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate In 1,4-dioxane; water at 90 - 100℃; for 12h; Inert atmosphere;
1.1 General procedure for preparation of intermediate j-5 and j-6
The appropriate boronic pinacol ester (2 eq) is added to a solution of intermediate j-3 (2 g, 7.1 mmol) in 1,4-dioxane/water (5:1). K2CO3 (2 eq) and PdCl2dppf (0.1 eq) are added to the solution. The resulting mixture is then heated in an oil bath at 90-100 °C for 12 h under N2. After cooling, water is added and the solution is extracted with EtOAc. The organic layers are dried over anhydrous Na2SO4 and evaporated in vacuum. The compound is obtained after purification by flash chromatography 1.1.1 N-(5-(4-formylphenyl)-[1,2,4]triazolo[1,5-a]pyridin-2 yl) cyclopropane carboxamide (j-5) Yield: 75% (1.63 g), brown solid.1H NMR (400 MHz, DMSO-d6) δH 11.13 (s, 1H), 10.12 (s, 1H), 8.25 (d, J = 8.4 Hz, 2H), 8.09 (d, J = 8.4 Hz, 2H), 7.92 - 7.64 (m, 2H), 7.42 (m, 1H), 2.01 (s, 1H), 0.82 (d, J = 6.2 Hz, 4H); 13C NMR (100 MHz, DMSO-d6) δC 192.66, 171.23, 158.13, 150.25, 138.21, 137.22, 136.60, 130.22, 129.68, 129.25, 114.50, 114.31, 13.78, 7.62. HRMS calcd for C17H14N4O2, [M+H]+, 307.1196, found 307.1187.
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In water; toluene at 90℃; for 36h; Inert atmosphere;
1-3
Step 1. Combine M1(mg)2,6-dibromoanthracene,M2(mg)4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde and 86mg of Pd(PPh3)4 were added to a 100mL two-mouth circle In a bottom flask, in an argon atmosphere, 950mg Na2CO3 dissolved in 8mL deionized water and 25mL toluene were sequentially injected into a two-neck round bottom flask, stirred at 90°C for 36 hours, and cooled to room temperature. Among them, the values of M1 and M2 See Table 1.Step 2: Add 20 mL of cooling water at a temperature of 0°C to the system obtained in Step 1, so as to obtain precipitation in the system;Step 3. Take out the precipitate obtained in step 2 and purify it by physical vapor transmission method to obtain a light yellow solid as BFPA. The method to take out the precipitate obtained in step 2 is: filter the system obtained in step 2 to obtain a solid precipitate, and remove the solid The precipitate is immersed in dichloromethane for extraction, and then filtered and washed with saturated sodium chloride solution (water as the solvent) to wash the solid precipitate, and finally the saturated sodium chloride solution is removed by suction filtration under reduced pressure to form the precipitate.
S-(trifluoromethyl) 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzothioate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
24%
With disodium hydrogenphosphate; tetrakis(tetrabutylammonium)decatungstate(VI); In acetonitrile; at 20.0℃; for 96.0h;Inert atmosphere; Sealed tube; Irradiation;
General procedure: To a 8 mL glass vial was added TBADT (54.4 mg, 0.016 mmol, 8 mol %), aldehydes (0.2 mmol, 1.0 equiv), 6a (148.3 mg, 0.6 mmol, 3.0 equiv), Na2HPO4 (42.6 mg, 0.3 mmol, 1.5 equiv) and 0.5mL of CH3CN. The reaction mixture was degassed by bubbling with Ar for 15 s with an outlet needle and the vial was sealed with PTFE cap. The mixture was then stirred rapidly and irradiated with a 390 nm Blue LED (approximately 2 cm away from the light source) at room temperature for 96 h. Purification of the crude product by flash chromatography on silica gelusing the indicated solvent system afforded the desired product.
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate In 1,4-dioxane; water at 25 - 80℃; for 2h; Inert atmosphere;
2.1 Step 1: 4-(2-methyl-1-oxo-1,2-dihydro-2,7-naphthyridin-4-yl)benzaldehyde (E37- 2)
To a solution of 4-bromo-2-methyl-2,7-naphthyridin-1(2H)-one (Intermediate 5, 3 g, 12.55 mmol) and 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde (E37-1, 2.07 g, 13.8 mmol) in a mixture of 1,4-dioxane (25 ml) and water (5 ml) under a nitrogen atmosphere was added Cs2CO3 (8.18 g, 25.10 mmol) and Pd(dppf)Cl2 (918.19 mg, 1.25 mmol) at 25 °C. The RM was stirred at 80 °C for 2 h. The mixture was filtered, the solids were triturated with EtOAc, filtered and dried, yielding the title compound 4-(2-methyl-1- oxo-1,2-dihydro-2,7-naphthyridin-4-yl)benzaldehyde, E37-2, as a solid, which was used for the next step without further purification. Method LCMS WX2: Rt = 0.56 min; [M+H]+ = 264.
1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-5-bromo-1,2-pentadiene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
57%
With [Au(1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene)(bis-(trifluoromethanesulfonyl)imidate)]; 1-methyl-1,2,3,4-tetrahydroisoquinoline In 2,2,2-trifluoroethanol at 25℃; for 48h; Schlenk technique; Inert atmosphere; Molecular sieve;
2-(3-(isocyanomethyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane[ No CAS ]
[ 128376-64-7 ]
[ 214360-73-3 ]
2-fluoro-N-(2-oxo-2-((3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl)amino)-1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)ethyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
68%
Stage #1: 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde; 2-(4-Aminophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In 2,2,2-trifluoroethanol at 65℃; for 0.25h; Microwave irradiation;
Stage #2: 2-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoic acid; 2-(3-(isocyanomethyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In 2,2,2-trifluoroethanol at 65℃; for 2h; Microwave irradiation;
2-(3-(isocyanomethyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane[ No CAS ]
[ 128376-64-7 ]
[ 214360-73-3 ]
2-fluoro-N-(2-oxo-2-((3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl)amino)-1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)ethyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
69%
Stage #1: 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde; 2-(4-Aminophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In 2,2,2-trifluoroethanol at 65℃; for 0.25h; Microwave irradiation;
Stage #2: 2-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoic acid; 2-(3-(isocyanomethyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In 2,2,2-trifluoroethanol at 65℃; for 2h; Microwave irradiation;
Stage #1: 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde; 2-(4-Aminophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In 2,2,2-trifluoroethanol at 65℃; for 0.25h; Microwave irradiation;
Stage #2: 2-(3-(isocyanomethyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane; C11H15BO5 In 2,2,2-trifluoroethanol at 65℃; for 2h; Microwave irradiation;
With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In tetrahydrofuran; lithium hydroxide monohydrate at 60℃; for 24h; Inert atmosphere;
1.1 (1) Synthesis of compound 1:
Tris(4-bromophenyl)amine (500 mg, 1.04 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl) Benzaldehyde (868mg, 3.74mmol), potassium carbonate (4.30g, 31.20mmol), tetrahydrofuran/water (9mL/3mL) and tetrakis(triphenylphosphine)palladium (109mg, 0.094mmol) were added to a 35mL pressure-resistant reaction flask , after freezing and deoxygenation in liquid nitrogen, the reaction was carried out under nitrogen protection at 60 °C for 24 hours.After the reaction, it was cooled to room temperature, tetrahydrofuran was removed by rotary evaporation, washed with dichloromethane and water in turn, dried with anhydrous sodium sulfate, and the solvent was rotary dried to obtain a crude product.Column chromatography (eluent: petroleum ether/dichloromethane=1/10, v/v) gave yellow-green compound 1 (530 mg) in 92% yield.
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