Name: 267221-90-9|Tris(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amine|98%
Brand: Ambeed
SKU: A460305
Price: 14.0 USD
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Rating: 90 (30 reviews)

1
[ 4316-58-9 ]
[ 73183-34-3 ]
[ 267221-90-9 ]

Yield	Reaction Conditions	Operation in experiment
89%	With anhydrous potassium acetate In 1,2-dimethoxyethane at 150℃; for 0.283333h; microwave irradiation;
87%	With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous potassium acetate In N,N-dimethyl-formamide at 90℃; Inert atmosphere; Schlenk technique;
71%	With sodium tertiary butoxide In toluene at 90℃; for 3h;	Synthesis of Intermediate 23; 84 g (330 mmol) of bis(pinacolato)diboron, 48.2 g (100 mmol) of Intermediate 22, 4.3 g (45 mmol) of t-BuONa, and 1.2 g (1.5 mmol) of Pd(dppf)2Cl2 were dissolved in 1000 mL of toluene and stirred at 90°C for 3 hours. After the reaction was completed, the reaction product was cooled to room temperature and extracted three times with distilled water and 500 ml of diethylether. An organic layer was collected and dried using magnesium sulfate to evaporate the solvent. The residue was separated and purified using silica gel column chromatography to obtain 44.2 g (yield: 71%) of Intermediate 23. This compound was identified using HR-MS.

64%	With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous potassium acetate In 1,4-dioxane for 24h; Reflux; Inert atmosphere;
63%	Stage #1: tri(p-bromophenyl)amine; 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl-4',4',5',5'-tetramethyl-1,3,2-dioxaborolane With anhydrous potassium acetate In 1,4-dioxane for 0.5h; Cooling with liquid nitrogen; Stage #2: With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride at 90℃; for 48h;	6 Example 6 Bromo-triphenylamine (0.65g, 5mmol),bis(pinacolato)diboron(3.6g, 15mmol),Potassium acetate (0.78g, 8mmol),Add 100mL dioxane to a 250mL round bottom flask and stir well and degas under liquid nitrogen freezing conditions for 30 minutes. After degassing is successful, add the catalyst Pd(dppf)Cl2 (90mg, 0.1mmol),Degas again twice to remove all oxygen in the reaction system. Finally, the round bottom flask was refluxed and heated in an oil bath at 90°C for 48 hours. After the reaction is completed, it is cooled to room temperature, deionized water and dichloromethane are added, and the mixture is stirred and extracted. The organic phase after the extraction and an appropriate amount of silica gel powder are added to a spin-type bottle and spin-dried. Finally, column chromatography was performed with petroleum ether: dichloromethane=10:1 as the eluent to obtain the product pinacol borate triphenylamine (1.96g, yield 63%).
61%	With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); zinc(II) diacetate dihydrate In dimethyl sulfoxide at 110℃; for 72h; Schlenk technique; Inert atmosphere; Darkness;
59%	With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous potassium acetate In 1,4-dioxane at 85℃;
59%	With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous potassium acetate In 1,4-dioxane at 85℃; Inert atmosphere; Schlenk technique;
59%	With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride In 1,4-dioxane at 85℃; for 12h; Inert atmosphere;
53%	With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous potassium acetate In 1,4-dioxane for 16h; Inert atmosphere; Reflux;	Synthesis of TPA-Bpin [41]. General procedure: A mixture of [1,1′ -Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.20 g, 0.27 mmol), bis(pinacolato)diboron (2.44 g, 9.60 mmol), 4-bromo-N,N-diphenylamine (2.56g, 8.00 mmol), KOAc (2.16 g, 22.00 mmol) and dehydrated 1,4-dioxane(100 mL) in a round bottom flask was refluxed under argon atmospherefor 16 h. The reaction mixtures were concentrated, extracted bydichloromethane, and purified by column chromatography (petroleumether/dichloromethane = 10/4, v/v) to afford the white solids with ayield of 60% (1.78 g).
52%	With palladium bis[bis(diphenylphosphino)ferrocene] dichloride; anhydrous potassium acetate In N,N-dimethyl-formamide at 85℃; for 12h;
20%	With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous potassium acetate In 1,4-dioxane at 85℃; for 12h; Inert atmosphere;
	With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous Sodium acetate at 85℃; for 36h; Inert atmosphere;	1.4 4) Synthesis of TPA-B (Compound 4) Under a nitrogen atmosphere, tris (4-bromophenyl) amine (4.82 g, 10 mmol) was added to a 250 mL two-necked flask bis(pinacolato) diborane(10.16 g, 40 mmol),Sodium acetate (19.6g, 200mmol), 2,4_ dioxane 120mL, catalyst bis (diphenylphosphino) ferrocene palladium chloride (82mg, 0. lmmol), warmed to 85 ° C.One and a half days of reaction, cooled to room temperature. The solvent is decanted, the reaction is poured into methylene chloride, extracted with water, dried over anhydrous sodium sulfate. The crude product was isolated on a silica gel column and a mixture of petroleum ether and ethyl acetate (8: 1) as eluent to give a white powder.
	With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous potassium acetate In 1,4-dioxane at 110℃; for 16h; Inert atmosphere;	2 Preparation of Tribenzoate tripropylamine Tribromo triphenylamine (5 g, 10.37 mmol), methyl acetate (3.05 g, 31.12 mmol) and bisboronate (10.54 g, 41.49 mmol) were added to a 250 mL two neck flask under argon atmosphere,1,4-dioxane was added for complete dissolution,Further [1,1'-bis (diphenylphosphino) ferrocene] palladium dichloride (379.51 mg, 518.67 μmol)The temperature was raised to 110 ° C and reacted for 16 hours.Extraction with ether,The ether phase was washed with saturated aqueous sodium chloride solution,Dried over anhydrous magnesium sulfate,Evaporate the solvent,The product was purified by column chromatography using petroleum ether as eluent,Got a white solid.
	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; anhydrous potassium acetate; dicyclohexyl[2’,4’,6’-tris(propan-2-yl)[1,1’-biphenyl]-2-yl]phosphane In tetrahydrofuran at 85℃; for 2h; Inert atmosphere;	2.5 4.2.2 4-methyl-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-N-(p-tolyl)aniline (4a) General procedure: A mixture of 3a (352 mg, 1.00 mmol), bis(pinacolato)diboron (257 mg, 1.01 mmol), Pd2(dba)3 (dba = dibenzylideneacetone; 14 mg, 0.015 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (Xphos; 29 mg, 0.061 mmol), KOAc (0.29 g, 3.0 mmol) and THF (3 mL) under argon atmosphere was heated at 85 °C for 2 h. After cooled down to room temperature, the reaction was diluted with EtOAc (10 mL) and washed with water (2 * 20 mL). The organic layer was dried over anhydrous Na2SO4 and evaporated in vacuum to afford the crude product of 4a which was used in the further step.

Reference： [1]Appukkuttan, Prasad; Van Der Eycken, Erik; Dehaen, Wim [Synlett, 2003, # 8, p. 1204 - 1206]
[2]Rocard, Lou; Hatych, Danylo; Chartier, Thomas; Cauchy, Thomas; Hudhomme, Piétrick [European Journal of Organic Chemistry, 2019, vol. 2019, # 47, p. 7635 - 7643]
[3]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - EP2292603, 2011, A1 Location in patent: Page/Page column 39
[4]Zhang, Youming; Bao, Xichang; Xiao, Manjun; Tan, Hua; Tao, Qiang; Wang, Yafei; Liu, Yu; Yang, Renqiang; Zhu, Weiguo [Journal of Materials Chemistry A, 2015, vol. 3, # 2, p. 886 - 893]
[5]Current Patent Assignee: NANCHANG WANJI TECH - CN113173950, 2021, A Location in patent: Paragraph 0034-0036
[6]Gao, Zhao; Hu, Xiao; Qiu, Shuai; Song, Xin; Tian, Wei; Yuan, Hongxing [Chemical Communications, 2022, vol. 58, # 29, p. 4647 - 4650]
[7]Location in patent: experimental part Wang, Guan; Pu, Kan-Yi; Zhang, Xinhai; Li, Kai; Wang, Long; Cai, Liping; Ding, Dan; Lai, Yee-Hing; Liu, Bin [Chemistry of Materials, 2011, vol. 23, # 20, p. 4428 - 4434]
[8]Liu, Xin; Xie, Yuan; Zhao, Haobin; Cai, Xinyi; Wu, Hongbin; Su, Shi-Jian; Cao, Yong [New Journal of Chemistry, 2015, vol. 39, # 11, p. 8771 - 8779]
[9]Ambili; Sasikumar, Devika; Hridya; Hariharan, Mahesh [Chemistry - A European Journal, 2019, vol. 25, # 8, p. 1992 - 2002]
[10]Ding, Guan-Yu; Zang, Chun-Xiu; Zhang, Han; Su, Zhong-Min; Li, Guang-Fu; Wen, Li-Li; Han, Xu; Xie, Wen-Fa; Shan, Guo-Gang [Dyes and Pigments, 2021, vol. 192]
[11]You, Fei; Zhou, Xingbao; Huang, Hongyan; Liu, You; Liu, Sizhou; Shao, Jinjun; Zhao, Baomin; Qin, Tianshi; Huang, Wei [New Journal of Chemistry, 2018, vol. 42, # 18, p. 15079 - 15087]
[12]Yang, Ji; Tan, Haoqi; Li, Dongyu; Jiang, Tao; Gao, Yuting; Li, Bo; Qu, Xue; Hua, Jianli [RSC Advances, 2016, vol. 6, # 63, p. 58434 - 58442]
[13]Current Patent Assignee: WUHAN INSTITUTE OF TECHNOLOGY - CN104341411, 2017, B Location in patent: Paragraph 0034; 0041-0042
[14]Current Patent Assignee: SOUTH CHINA UNIVERSITY OF TECHNOLOGY - CN107286175, 2017, A Location in patent: Paragraph 0076-0079
[15]Eiamprasert, Utt; Sudchanham, Jutarat; Surawatanawong, Panida; Pakawatpanurut, Pasit; Kiatisevi, Supavadee [Journal of Photochemistry and Photobiology A: Chemistry, 2018, vol. 352, p. 86 - 97]

2
[ 61676-62-8 ]
[ 4316-58-9 ]
[ 267221-90-9 ]

Yield	Reaction Conditions	Operation in experiment
89%	Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃;
64%	Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at -78 - 20℃; Inert atmosphere;	General procedure A for synthesis of triphenylamine substituted boronic ester (Scheme 1) General procedure: 4-Bromo substituted triphenylamine was dissolved in dry THF under nitrogen atmosphere and it was cooled to -78 ° C . n-BuLi was added with syringe and kept at -78 ° C for one hour. 2-Isopropoxy-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane was added dropwise. After addition, the solution was allowed to warm up to room temperature for overnight reaction. After quenching of the reaction with ammonium chloride solution, the water layer was extracted with chloroform and the combined organic layer was dried over MgSO4. After the remove of the solvent under reduced pressure, the residue was purified by silica gel column chromatography (petroleum ether/dichloromethane 1:1) to afford the product as white solids.
63%	Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran

62%	Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere;
62%	Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere;
60%	Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran; hexane at -78 - -65℃; for 1.5h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -65 - 20℃; Inert atmosphere;
60%	Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran; hexane at -78 - 0℃; for 1.25h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere;
57%	Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at -78 - 20℃; for 13h; Inert atmosphere;
55%	Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at -78 - 20℃; for 12h; Inert atmosphere;
55%	Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃; for 49h; Inert atmosphere;	2.2.1.1 Synthesis of tris(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amine 1.93g (4.00mmol) Of tris(4-bromophenyl)amine was dissolved in anhydrous tetrahydrofuran (THF) (60mL), the solution was degassed and stirred at -78°C. 4.86mL (13.61mmol) Of n-butyllithium solution (n-BuLi, 2.8M in hexane) was added to the above mixture under Ar atmosphere and the resulting solution was stirred for 2hat -78°C. 5.83mL (28.58mmol) Of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added to the solution and the mixture was kept at -78°C for another 1h and then stirred at room temperature for 48h. The reaction was quenched with water, and the organic layer was extracted with dichloromethane (DCM). After dried over MgSO4, the solution was concentrated and the solvent mixture of DCM/hexane (3:2) was used as eluent for silica gel column chromatography to isolate the product. The obtained product was further purified by recrystallization from chloroform (CHCl3)/ethanol to give a white solid in 55% yield. 1H NMR (600MHz, C2D2Cl4): δ (ppm) 1.30 (s, 36H), 7.03 (d, 6H), 7.64 (d, 6H). MS (APLI): m/z calcd 623.3778; found 623.3667.
54%	Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran at -80℃; for 1h; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at -80 - 20℃;
34.8%	Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃;
15.5%	Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran at -78℃; for 2h; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at -78 - 20℃; for 38h;
	Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran at -78 - 20℃; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran for 24h;
	With n-butyllithium In tetrahydrofuran at -78℃; for 16h;
	With n-butyllithium In tetrahydrofuran

Reference： [1]Xiao, Wen-Jing; Wang, Yong; Wang, Wen-Rui; Li, Jia; Wang, Jiandong; Xu, Zi-Wen; Li, Jingjing; Yao, Jianhua; Li, Wei-Shi [Macromolecules, 2020, vol. 53, # 7, p. 2454 - 2463]
[2]Chen, Fengkun; Fu, Xiangyu; Zhang, Jie; Wan, Xinhua [Electrochimica Acta, 2013, vol. 99, p. 211 - 218]
[3]Liu, Cheng-Fang; Jiu, Yuanda; Wang, Jianyun; Yi, Jianpeng; Zhang, Xin-Wen; Lai, Wen-Yong; Huang, Wei [Macromolecules, 2016, vol. 49, # 7, p. 2549 - 2558]
[4]Location in patent: experimental part Sahu, Duryodhan; Tsai, Chia-Hua; Wei, Hung-Yu; Ho, Kuo-Chuan; Chang, Feng-Chih; Chu, Chih-Wei [Journal of Materials Chemistry, 2012, vol. 22, # 16, p. 7945 - 7953]
[5]Kolaczkowski, Matthew A.; He, Bo; Liu, Yi [Organic Letters, 2016, vol. 18, # 20, p. 5224 - 5227]
[6]Guo, Lei; Li, King Fai; Wong, Man Shing; Cheah, Kok Wai [Chemical Communications, 2013, vol. 49, # 34, p. 3597 - 3599]
[7]Hu, Zhao; Li, Xiao-Dong; Zhang, Wenjun; Liang, Aihui; Ye, Dandan; Liu, Zhitian; Liu, Jing; Liu, Yanjiao; Fang, Junfeng [RSC Advances, 2014, vol. 4, # 11, p. 5591 - 5597]
[8]Location in patent: experimental part Shi, Liqi; He, Chao; Zhu, Defeng; He, Qingguo; Li, Yang; Chen, Yan; Sun, Yuxi; Fu, Yanyan; Wen, Dan; Cao, Huimin; Cheng, Jiangong [Journal of Materials Chemistry, 2012, vol. 22, # 23, p. 11629 - 11635]
[9]Metri; Sallenave; Beouch; Plesse; Goubard; Chevrot [Tetrahedron Letters, 2010, vol. 51, # 50, p. 6673 - 6676]
[10]Dong, Wenyue; Ma, Zhihua; Duan, Qian; Fei, Teng [Dyes and Pigments, 2018, vol. 159, p. 128 - 134]
[11]Cremer, Jens; Baeuerle, Peter [Journal of Materials Chemistry, 2006, vol. 16, # 9, p. 874 - 884]
[12]Fan, Congbin; Wang, Xiaomei; Ding, Ping; Wang, Jingjing; Liang, Zuoqin; Tao, Xutang [Dyes and Pigments, 2012, vol. 95, # 3, p. 757 - 767]
[13]Li, Zhong'An; Ye, Tenglin; Tang, Sun; Wang, Can; Ma, Dongge; Li, Zhen [Journal of Materials Chemistry C, 2015, vol. 3, # 9, p. 2016 - 2023]
[14]Gudeika, Dalius; Grazulevicius, Juozas Vidas; Sini, Gjergji; Bucinskas, Audrius; Jankauskas, Vygintas; Miasojedovas, Arunas; Jursenas, Saulius [Dyes and Pigments, 2014, vol. 106, p. 58 - 70]
[15]Bui, Thanh-Tuân; Shah, Said Karim; Sallenave, Xavier; Abbas, Mamatimin; Sini, Gjergji; Hirsch, Lionel; Goubard, Fabrice [RSC Advances, 2015, vol. 5, # 61, p. 49590 - 49597]
[16]Lv, Yaokang; Yang, Xing; Du, Weishi; Ma, Peihua; Wang, Hu; Bonnefont, Antoine; Wright, Dominic S.; Ruhlmann, Laurent; Zhang, Cheng [ChemSusChem, 2020, vol. 13, # 15, p. 3844 - 3854]

3
[ 850881-16-2 ]
[ 267221-90-9 ]
tris{4-[8-(2-(2,6-diisopropylphenyl)-1H-benzo[5,10]anthra[2,1,9-def]isoquinoline-1,3(2H)-dione)-4,3'-dihexyl-2,2'-bithien-5'-yl]phenyl}amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	With sodium hydroxide; tetrakis(triphenylphosphine) palladium⁽⁰⁾ In 1,2-dimethoxyethane at 80℃; for 24h;

Reference： [1]Cremer, Jens; Baeuerle, Peter [Journal of Materials Chemistry, 2006, vol. 16, # 9, p. 874 - 884]

4
[ 883718-17-0 ]
[ 267221-90-9 ]
tris-[4-(3,4'-dihexyl-5'-methyl-2,2'-bithien-5-yl)phenyl]amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With potassium phosphate; tris(dibenzylideneacetone)dipalladium ⁽⁰⁾; tri tert-butylphosphoniumtetrafluoroborate In 1,2-dimethoxyethane at 20℃; for 6h;

Reference： [1]Cremer, Jens; Baeuerle, Peter [Journal of Materials Chemistry, 2006, vol. 16, # 9, p. 874 - 884]

5
[ 603-34-9 ]
[ 267221-90-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: 86 percent / bromine / CHCl₃ / 1 h 2.1: n-BuLi / tetrahydrofuran / 1 h / -80 °C 2.2: 54 percent / tetrahydrofuran / -80 - 20 °C
	Multi-step reaction with 2 steps 1.1: N-Bromosuccinimide / N,N-dimethyl-formamide / 12 h / 0 - 20 °C 2.1: n-butyllithium / tetrahydrofuran; hexane / 2 h / -78 °C / Inert atmosphere 2.2: -78 - 20 °C / Inert atmosphere
	Multi-step reaction with 2 steps 1.1: bromine / chloroform / 24 h / 20 °C / UV-irradiation 2.1: n-butyllithium / tetrahydrofuran / 1 h / -78 °C / Inert atmosphere 2.2: 13 h / -78 - 20 °C / Inert atmosphere

	Multi-step reaction with 2 steps 1.1: bromine / chloroform / 20 °C / Cooling with ice 2.1: n-butyllithium / tetrahydrofuran / 2 h / -78 °C 2.2: 38 h / -78 - 20 °C
	Multi-step reaction with 2 steps 1: N-Bromosuccinimide / N,N-dimethyl-formamide 2: n-butyllithium / tetrahydrofuran

Reference： [1]Cremer, Jens; Baeuerle, Peter [Journal of Materials Chemistry, 2006, vol. 16, # 9, p. 874 - 884]
[2]Sahu, Duryodhan; Tsai, Chia-Hua; Wei, Hung-Yu; Ho, Kuo-Chuan; Chang, Feng-Chih; Chu, Chih-Wei [Journal of Materials Chemistry, 2012, vol. 22, # 16, p. 7945 - 7953]
[3]Shi, Liqi; He, Chao; Zhu, Defeng; He, Qingguo; Li, Yang; Chen, Yan; Sun, Yuxi; Fu, Yanyan; Wen, Dan; Cao, Huimin; Cheng, Jiangong [Journal of Materials Chemistry, 2012, vol. 22, # 23, p. 11629 - 11635]
[4]Li, Zhong'An; Ye, Tenglin; Tang, Sun; Wang, Can; Ma, Dongge; Li, Zhen [Journal of Materials Chemistry C, 2015, vol. 3, # 9, p. 2016 - 2023]
[5]Lv, Yaokang; Yang, Xing; Du, Weishi; Ma, Peihua; Wang, Hu; Bonnefont, Antoine; Wright, Dominic S.; Ruhlmann, Laurent; Zhang, Cheng [ChemSusChem, 2020, vol. 13, # 15, p. 3844 - 3854]

6
[ 267221-90-9 ]
[ 763114-96-1 ]
[ 1260162-09-1 ]

Yield	Reaction Conditions	Operation in experiment
61%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water at 80℃; for 42h; Inert atmosphere;

Reference： [1]Metri; Sallenave; Beouch; Plesse; Goubard; Chevrot [Tetrahedron Letters, 2010, vol. 51, # 50, p. 6673 - 6676]

7
[ 936029-86-6 ]
[ 267221-90-9 ]
[ 1256354-84-3 ]

Yield	Reaction Conditions	Operation in experiment
43.5%	With potassium phosphate; tri tert-butylphosphoniumtetrafluoroborate In water; toluene at 120℃; for 24h; Inert atmosphere;

Reference： [1]Location in patent: experimental part Zhang, Jing; Deng, Dan; He, Chang; He, Youjun; Zhang, Maojie; Zhang, Zhi-Guo; Zhang, Zhanjun; Li, Yongfang [Chemistry of Materials, 2011, vol. 23, # 3, p. 817 - 822]

8
[ 1336877-96-3 ]
[ 267221-90-9 ]
4,4',4"-tris(4-(2-(4-(benzo[d]thiazol-2-yl)phenyl)-9,9-bis(6-bromohexyl)fluoren-7-yl))phenylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
18%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; tetrabutylammomium bromide; sodium carbonate In water; toluene at 100℃; for 48h;

Reference： [1]Location in patent: experimental part Wang, Guan; Pu, Kan-Yi; Zhang, Xinhai; Li, Kai; Wang, Long; Cai, Liping; Ding, Dan; Lai, Yee-Hing; Liu, Bin [Chemistry of Materials, 2011, vol. 23, # 20, p. 4428 - 4434]

9
[ 1308671-90-0 ]
[ 267221-90-9 ]
[ 1373340-84-1 ]

Reference： [1]Journal of Materials Chemistry A,2015,vol. 3,p. 886 - 893
[2]Chemical Communications,2012,vol. 48,p. 4773 - 4775
[3]Journal of Materials Chemistry,2012,vol. 22,p. 7945 - 7953

10
[ 1192758-95-4 ]
[ 267221-90-9 ]
[ 1380608-75-2 ]

Yield	Reaction Conditions	Operation in experiment
55.4%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In water; toluene for 48h; Inert atmosphere; Reflux;

Reference： [1]Location in patent: experimental part Shi, Liqi; He, Chao; Zhu, Defeng; He, Qingguo; Li, Yang; Chen, Yan; Sun, Yuxi; Fu, Yanyan; Wen, Dan; Cao, Huimin; Cheng, Jiangong [Journal of Materials Chemistry, 2012, vol. 22, # 23, p. 11629 - 11635]

11
[ 89972-76-9 ]
[ 267221-90-9 ]
4,4',4'’-tri[4-(2,2':6',2'’-terpyridinyl)]phenyltriphenylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75.6%	With tetrakis-(triphenylphosphine)-palladium; anhydrous sodium carbonate In tetrahydrofuran; lithium hydroxide monohydrate at 70℃; for 15h;
52%	With potassium carbonate In tetrahydrofuran; lithium hydroxide monohydrate at 70℃; for 48h; Schlenk technique; Inert atmosphere; Darkness;

Reference： [1]Fan, Congbin; Wang, Xiaomei; Ding, Ping; Wang, Jingjing; Liang, Zuoqin; Tao, Xutang [Dyes and Pigments, 2012, vol. 95, # 3, p. 757 - 767]
[2]Gao, Zhao; Hu, Xiao; Qiu, Shuai; Song, Xin; Tian, Wei; Yuan, Hongxing [Chemical Communications, 2022, vol. 58, # 29, p. 4647 - 4650]

12
[ 161726-69-8 ]
[ 267221-90-9 ]
C₅₇H₃₃NO₃S₉ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In water; toluene at 110℃; for 16h; Inert atmosphere;

Reference： [1]Lin, Yuze; Zhang, Zhi-Guo; Bai, Huitao; Li, Yongfang; Zhan, Xiaowei [Chemical Communications, 2012, vol. 48, # 77, p. 9655 - 9657]

13
[ 76-09-5 ]
C₁₈H₁₂B₃Cl₆N [ No CAS ]
[ 267221-90-9 ]

Yield	Reaction Conditions	Operation in experiment
460 mg	With triethylamine at 0 - 20℃; for 1h; Inert atmosphere;

Reference： [1]Bagutski, Viktor; Del Grosso, Alessandro; Carrillo, Josue Ayuso; Cade, Ian A.; Helm, Matthew D.; Lawson, James R.; Singleton, Paul J.; Solomon, Sophia A.; Marcelli, Tommaso; Ingleson, Michael J. [Journal of the American Chemical Society, 2013, vol. 135, # 1, p. 474 - 487]

14
[ 1430084-03-9 ]
[ 267221-90-9 ]
[ 1430084-09-5 ]

Yield	Reaction Conditions	Operation in experiment
85%	With palladium diacetate; potassium carbonate; triphenylphosphine In ethanol; water; toluene for 24h; Inert atmosphere; Reflux;

Reference： [1]Guo, Lei; Li, King Fai; Wong, Man Shing; Cheah, Kok Wai [Chemical Communications, 2013, vol. 49, # 34, p. 3597 - 3599]

15
[ 1373359-09-1 ]
[ 267221-90-9 ]
tris(4-bromophenyl)amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%	With palladium diacetate; potassium carbonate; triphenylphosphine In ethanol; water; toluene for 48h; Inert atmosphere; Reflux;

Reference： [1]Guo, Lei; Li, King Fai; Wong, Man Shing; Cheah, Kok Wai [Chemical Communications, 2013, vol. 49, # 34, p. 3597 - 3599]

16
[ 1430084-01-7 ]
[ 267221-90-9 ]
tris(4-bromophenyl)amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With palladium diacetate; potassium carbonate; triphenylphosphine In ethanol; water; toluene for 48h; Inert atmosphere; Reflux;

Reference： [1]Guo, Lei; Li, King Fai; Wong, Man Shing; Cheah, Kok Wai [Chemical Communications, 2013, vol. 49, # 34, p. 3597 - 3599]

17
[ 1440066-24-9 ]
[ 267221-90-9 ]
[ 1440066-36-3 ]

Yield	Reaction Conditions	Operation in experiment
62%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In ethanol; water; toluene for 6h; Inert atmosphere; Reflux;	6 General procedure B for synthesis of triphenylamine-anthraquinone imide product General procedure: To a mixture of 6-bromo substituted anthraquinone imide 4, Na2CO3 and Pd(PPh3)4, compound 2, toluene, ethanol and water were added under nitrogen. The reaction mixture was heated to reflux and kept for 6h. After cooled to room temperature, the water layer was extracted with dichloromethane and the combined organic layer was dried over MgSO4. Volatile solvent was removed under reduced pressure. Then, the raw product was purified by silica gel column chromatography (petroleum ether/dichloromethane 1:2) as solids.

Reference： [1]Chen, Fengkun; Fu, Xiangyu; Zhang, Jie; Wan, Xinhua [Electrochimica Acta, 2013, vol. 99, p. 211 - 218]

18
[ 14282-76-9 ]
[ 267221-90-9 ]
[ 1447089-38-4 ]

Yield	Reaction Conditions	Operation in experiment
94%	With tetrakis(triphenylphosphine) palladium(0); Aliquat 336; potassium carbonate; In water; toluene; at 80℃; for 80h;Schlenk technique; Inert atmosphere;	General procedure: In a dryschlenk equipped with a magnetic stir bar, <strong>[14282-76-9]<strong>[14282-76-9]2-bromo-3-methylthiophen</strong>e</strong>(324 mg, 1.885 mmol, 4.5 equiv.), tris(4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolane)phenyl)amine(261 mg, 0.419 mmol, 1.0 equiv.), distillated toluene (100 mL) anddeionized water (40 mL) were charged. The mixture was thendegassed by argon purging for 20 min then K2CO3 (11 g, 80mmol), aliquat 336 (5 drops), and Pd(PPh3)4 (49 mg, 0.042mmol, 0.1 equiv.) were added. After purging by argon for further 15 min, themixture was refluxed for 80 h under argon and allowed to cool to roomtemperature. The mixture was diluted with water (100 mL) and was extracted withCH2Cl2 (3x50 mL). The organic layers were combined,washed with brine and water, dried over anhydrous MgSO4, filtered,and concentrated under reduced pressure. The crude product was purified bycolumn chromatography eluting with CH2Cl2/cyclohexane(2/8 3/7v/v) to yield 8 as a pale yellowsolid (210 mg, 94 % yield). 1H NMR (DMSO-d6, d/ppm): 7.45 (d, 6 H, J = 8.5 Hz), 7.42 (d, 3 H,J = 5.0 Hz), 7.15 (d, 6 H, J = 8.5 Hz), 6.98 (d, 3 H, J = 5.0 Hz), 2.30 (s, 9H). 13C NMR (DMSO-d6, d/ppm): 145.7, 136.5, 132. 7, 131.6, 129.7,129.0, 124.0, 123.8, 14.9.

Reference： [1]Tetrahedron Letters,2013,vol. 54,p. 4277 - 4280
[2]RSC Advances,2015,vol. 5,p. 49590 - 49597

19
[ 14282-76-9 ]
[ 267221-90-9 ]
[ 1447089-41-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: potassium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾; Aliquat 336 / toluene; water / 80 h / 80 °C / Schlenk technique; Inert atmosphere 2: N-Bromosuccinimide / N,N-dimethyl-formamide / 3 h / 0 - 20 °C / Inert atmosphere

Reference： [1]Bui, Thanh-Tuan; Beouch, Layla; Sallenave, Xavier; Goubard, Fabrice [Tetrahedron Letters, 2013, vol. 54, # 32, p. 4277 - 4280]

20
[ 1403579-44-1 ]
[ 267221-90-9 ]
[ 1433812-45-3 ]

Yield	Reaction Conditions	Operation in experiment
70%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In water; toluene at 85℃; for 72h; Inert atmosphere;

Reference： [1]Hu, Zhao; Li, Xiao-Dong; Zhang, Wenjun; Liang, Aihui; Ye, Dandan; Liu, Zhitian; Liu, Jing; Liu, Yanjiao; Fang, Junfeng [RSC Advances, 2014, vol. 4, # 11, p. 5591 - 5597]

21
[ 1193092-32-8 ]
[ 267221-90-9 ]
[ 1605305-93-8 ]

Yield	Reaction Conditions	Operation in experiment
34%	With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water at 80℃; for 24h; Inert atmosphere;	2.1.1 4-(4-Diphenylaminophenyl)-N-ethylhexyl-1,8-naphthalimide (4) General procedure: The solution of 4-bromo-1,8-naphthalimide (1) (0.5 g, 1.29 mmol) and Pd(PPh3)2Cl2 (0.03 g, 0.04 mmol) in THF (15 mL) was purged with nitrogen, and the solution of 4-(diphenylamino)phenylboronic acid (0.37 g, 1.28 mmol) in THF (3 mL) and aqueous K2CO3 solution (1.70 g, 12.32 mmol) in H2O (2 mL) were added with a syringe. The reaction mixture was stirred at 80 °C for 24 h. After cooling down, the product was extracted with CH2Cl2, washed with water and dried over MgSO4. The solvent was evaporated to afford a crude product. After column chromatography on silica gel with the eluent mixture of ethyl acetate and hexane (1:8, V:V), compound 4 was obtained as yellow powder with the yield of 0.55 g (78%).

Reference： [1]Gudeika, Dalius; Grazulevicius, Juozas Vidas; Sini, Gjergji; Bucinskas, Audrius; Jankauskas, Vygintas; Miasojedovas, Arunas; Jursenas, Saulius [Dyes and Pigments, 2014, vol. 106, p. 58 - 70]

22
[ 1356240-65-7 ]
[ 267221-90-9 ]
C₁₅₀H₁₅₉N₇O₁₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
46%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In water; toluene at 110℃; Inert atmosphere;
46%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In water; toluene at 110℃; for 48h; Inert atmosphere;	1 Example 1 A 25 mL three-necked flask was charged with intermediate a(0.225 mmol, 175 mg),Intermediate b (0.075 mmol, 46 mg),Toluene (10 mL) and aqueous potassium carbonate (2 M, 5 mL);After removal of oxygen by argon for 30 min, tetrakis (triphenylphosphine) palladium was added under argon atmosphere(0.035 mmol, 40 mg),The mixture was refluxed at a temperature of 110 ° C48 hours after cooling to room temperature;The organic phase was extracted with dichloromethane,The resulting organic phase was then dried over anhydrous magnesium sulfate.After removal of the dichloromethane solvent using a rotary evaporator,Purification by silica gel column chromatography using dichloromethane as eluant gave a purple-black solid,Is a star-shaped three-dimensional conjugated molecule based on triphenylamine-perylene diimide.

Reference： [1]Lin, Yuze; Wang, Yifan; Wang, Jiayu; Hou, Jianhui; Li, Yongfang; Zhu, Daoben; Zhan, Xiaowei [Advanced Materials, 2014, vol. 26, # 30, p. 5137 - 5142]
[2]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES; Institute of Chemistry (in: CAS) - CN104650083, 2016, B Location in patent: Paragraph 0032; 0033; 0034; 0035

23
3-(5-bromothiophen-2-yl)-2,5-bis(2-ethylhexyl)-6-(5-(phenanthren-2-yl)thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione [ No CAS ]
[ 267221-90-9 ]
tris(4-(2,5-bis(2-ethylhexyl))-3-(5-(phenanthren-2-yl)thiophen-2-yl)-6-(thiophen-2-yl)-pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione)amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
42%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In ethanol; water; toluene at 80℃; for 24h; Inert atmosphere;

Reference： [1]Zhang, Youming; Bao, Xichang; Xiao, Manjun; Tan, Hua; Tao, Qiang; Wang, Yafei; Liu, Yu; Yang, Renqiang; Zhu, Weiguo [Journal of Materials Chemistry A, 2015, vol. 3, # 2, p. 886 - 893]

24
5’’-bromo-4’,4’’-dioctyl-2,2’:5’,2’’-trithiophene-5-carbaldehyde [ No CAS ]
[ 267221-90-9 ]
C₁₀₅H₁₂₉NO₃S₉ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; tetrabutylammomium bromide; sodium carbonate In water; toluene for 48h; Reflux;	2.4.1 Synthesis of TCHO3TTPA 5″-Bromo-4′,4″-dioctyl-[2,2′:5′,2″-terthiophene]-5-carbaldehyde (1 g, 1.73 mmol) and tris(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amine (0.3 g, 0.48 mmol), Pd(PPh3)4 (0.15 g, 0.13 mmol), tetrabutylammonium bromide(0.03 g, 0.09 mmol), toluene (20 mL), 2 mol/L Na2CO3aqueous solution (20 mL) were mixed together in a 100-mLround-bottom flask. The mixture was degassed and refluxedfor 48 h and then cooled down to room temperature. Waterwas added and the mixture was extracted with dichloromethane.The organic layer was washed successively withbrine and water, and then dried with Na2SO4. After the solventwas removed under reduced pressure, the crude productwas purified by flash chromatography, using dichloromethaneas eluent, to give TCHO3TTPA (0.72 g, 86%). 1HNMR (600 MHz, CDCl3): δ 9.86 (s, 3H), 7.67 (d, J=3.9 Hz,3H), 7.40 (d, J=8.5 Hz, 6H), 7.24 (s, 3H), 7.22 (d, J=3.6 Hz,6H), 7.20 (s, 3H), 7.06 (s, 3H), 2.84-2.75 (m, 6H),2.75-2.64 (m, 6H), 1.73-1.62 (m, 12H), 1.47-1.19 (m,60H), 0.89-0.86 (m, 18H). 13C NMR (150 MHz, CDCl3): δ182.43, 147.16, 146.54, 141.40, 140.45, 139.00, 138.36,137.45, 133.22, 132.99, 132.88, 130.05, 129.17, 128.92,128.90, 124.18, 123.86, 31.89, 30.97, 30.50, 29.54, 29.53,29.43, 29.41, 29.27, 28.83, 22.68, 14.13. MS (ACPI) m/z:Calcd. for C105H129NO3S9 [M]+: 1740.7492. Found:1740.7499.

Reference： [1]Zhou, Yuanhang; Chen, Weichao; Du, Zhengkun; Zhu, Dangqiang; Ouyang, Dan; Han, Liangliang; Yang, Renqiang [Science China Chemistry, 2015, vol. 58, # 2, p. 357 - 363]

25
6-(5'-bromo-[2,2'-bithiophen]-5-yl)-2-octyl-1H-benzo[de]isoquinoline-1,3(2H)-dione [ No CAS ]
[ 267221-90-9 ]
C₁₀₂H₉₀N₄O₆S₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
51%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tetrabutylammomium bromide; sodium hydrogencarbonate; tris-(o-tolyl)phosphine In water; toluene for 72h; Inert atmosphere; Reflux;	2.5.4. General procedure for the preparation of SM2-4 General procedure: A mixture of tris(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amine (0.16 g, 0.25 mmol), 2-4b (0.75 mmol), NaHCO3(0.2 g, 2.4 mmol), H2O (2 mL), toluene (50 mL), tetrabutylammonium bromide (TBAB, 16 mg, 0.05 mmol) was carefully degassed before and after Pd2(dba)3 (16 mg, 0.018 mmol) and P(o-tol)3 (50 mg, 0.16 mmol) were added. The mixture was stirred at reflux for 3 days under N2 atmosphere. After being cooled to room temperature, water (100 mL) was added and the resulted mixture was extracted with DCM (50 mL x 3). The collected organic layers were washed with brine (50 mL x 3), dried over anhydrous MgSO4, and evaporated to dryness. The residue was further purified using column chromatography.

Reference： [1]Zhang, Jicheng; Li, Guangwu; Kang, Chong; Lu, Heng; Zhao, Xiuxiu; Li, Cuihong; Li, Wenhua; Bo, Zhishan [Dyes and Pigments, 2015, vol. 115, p. 181 - 189]

26
N-octyl-4-{5-[5-(5-bromothien-2-yl)thien-2-yl]thien-2-yl}-1,8-naphthalimide [ No CAS ]
[ 267221-90-9 ]
C₁₁₄H₉₆N₄O₆S₉ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
25%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tetrabutylammomium bromide; sodium hydrogencarbonate; tris-(o-tolyl)phosphine In water; toluene for 72h; Inert atmosphere; Reflux;	2.5.4. General procedure for the preparation of SM2-4 General procedure: A mixture of tris(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amine (0.16 g, 0.25 mmol), 2-4b (0.75 mmol), NaHCO3(0.2 g, 2.4 mmol), H2O (2 mL), toluene (50 mL), tetrabutylammonium bromide (TBAB, 16 mg, 0.05 mmol) was carefully degassed before and after Pd2(dba)3 (16 mg, 0.018 mmol) and P(o-tol)3 (50 mg, 0.16 mmol) were added. The mixture was stirred at reflux for 3 days under N2 atmosphere. After being cooled to room temperature, water (100 mL) was added and the resulted mixture was extracted with DCM (50 mL x 3). The collected organic layers were washed with brine (50 mL x 3), dried over anhydrous MgSO4, and evaporated to dryness. The residue was further purified using column chromatography.

Reference： [1]Zhang, Jicheng; Li, Guangwu; Kang, Chong; Lu, Heng; Zhao, Xiuxiu; Li, Cuihong; Li, Wenhua; Bo, Zhishan [Dyes and Pigments, 2015, vol. 115, p. 181 - 189]

27
N-octyl-4-{5-[5-(5-bromothien-2-yl)-3,4-dioctylthien-2-yl]thien-2-yl}-1,8-naphthalimide [ No CAS ]
[ 267221-90-9 ]
C₁₆₂H₁₉₂N₄O₆S₉ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
45%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tetrabutylammomium bromide; sodium hydrogencarbonate; tris-(o-tolyl)phosphine In water; toluene for 72h; Inert atmosphere; Reflux;	2.5.4. General procedure for the preparation of SM2-4 General procedure: A mixture of tris(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amine (0.16 g, 0.25 mmol), 2-4b (0.75 mmol), NaHCO3(0.2 g, 2.4 mmol), H2O (2 mL), toluene (50 mL), tetrabutylammonium bromide (TBAB, 16 mg, 0.05 mmol) was carefully degassed before and after Pd2(dba)3 (16 mg, 0.018 mmol) and P(o-tol)3 (50 mg, 0.16 mmol) were added. The mixture was stirred at reflux for 3 days under N2 atmosphere. After being cooled to room temperature, water (100 mL) was added and the resulted mixture was extracted with DCM (50 mL x 3). The collected organic layers were washed with brine (50 mL x 3), dried over anhydrous MgSO4, and evaporated to dryness. The residue was further purified using column chromatography.

Reference： [1]Zhang, Jicheng; Li, Guangwu; Kang, Chong; Lu, Heng; Zhao, Xiuxiu; Li, Cuihong; Li, Wenhua; Bo, Zhishan [Dyes and Pigments, 2015, vol. 115, p. 181 - 189]

28
4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3-dioxolan-2-yl)-1,3,2-dioxaborolane [ No CAS ]
[ 4316-58-9 ]
[ 267221-90-9 ]

Yield	Reaction Conditions	Operation in experiment
70.3%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 80℃; for 24h; Inert atmosphere;

Reference： [1]Zhou, Pei; Dang, Dongfeng; Xiao, Manjun; Wang, Qiong; Zhong, Juan; Tan, Hua; Pei, Yong; Yang, Renqiang; Zhu, Weiguo [Journal of Materials Chemistry A, 2015, vol. 3, # 20, p. 10883 - 10889]

29
3-(7-bromobenzo[c][1,2,5]thiadiazol-4-yl)-9-octyl-9H-carbazole [ No CAS ]
[ 267221-90-9 ]
C₉₆H₉₀N₁₀S₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
48.15%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In ethanol; water; toluene at 80℃; for 24h; Inert atmosphere;

Reference： [1]Zhou, Pei; Dang, Dongfeng; Xiao, Manjun; Wang, Qiong; Zhong, Juan; Tan, Hua; Pei, Yong; Yang, Renqiang; Zhu, Weiguo [Journal of Materials Chemistry A, 2015, vol. 3, # 20, p. 10883 - 10889]

30
2-(7-bromobenzo[c][2,1,3]thiadiazol-4-yl)-9-octylcarbazole [ No CAS ]
[ 267221-90-9 ]
C₉₆H₉₀N₁₀S₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
50.6%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In ethanol; water; toluene at 80℃; for 24h; Inert atmosphere;

Reference： [1]Zhou, Pei; Dang, Dongfeng; Xiao, Manjun; Wang, Qiong; Zhong, Juan; Tan, Hua; Pei, Yong; Yang, Renqiang; Zhu, Weiguo [Journal of Materials Chemistry A, 2015, vol. 3, # 20, p. 10883 - 10889]

31
5-bromo-N,N-bis(4-methoxyphenyl)-3-methylthiophen-2-amine [ No CAS ]
[ 267221-90-9 ]
tris(4-(5-(4,4'-dimethoxydiphenylamino)-4-methyl-2-thiophenyl)phenyl)amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In toluene at 90℃; for 72h; Schlenk technique; Inert atmosphere;

Reference： [1]Bui, Thanh-Tuân; Shah, Said Karim; Sallenave, Xavier; Abbas, Mamatimin; Sini, Gjergji; Hirsch, Lionel; Goubard, Fabrice [RSC Advances, 2015, vol. 5, # 61, p. 49590 - 49597]

32
[ 267221-90-9 ]
[ 1447089-41-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate / toluene / 72 h / 90 °C / Schlenk technique; Inert atmosphere 2: N-Bromosuccinimide / N,N-dimethyl-formamide / 0 - 20 °C

Reference： [1]Bui, Thanh-Tuân; Shah, Said Karim; Sallenave, Xavier; Abbas, Mamatimin; Sini, Gjergji; Hirsch, Lionel; Goubard, Fabrice [RSC Advances, 2015, vol. 5, # 61, p. 49590 - 49597]

33
3-(7-(5-bromothiophen-2-yl)benzo[c][2,1,3]thiadiazol-4-yl)-9-octylcarbazole [ No CAS ]
[ 267221-90-9 ]
C₁₀₈H₉₆N₁₀S₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
43.3%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; potassium carbonate; tris-(o-tolyl)phosphine In toluene at 80℃; for 24h; Inert atmosphere;

Reference： [1]Zhou, Pei; Dang, Dongfeng; Wang, Qiong; Duan, Xiongwei; Xiao, Manjun; Tao, Qiang; Tan, Hua; Yang, Renqiang; Zhu, Weiguo [Journal of Materials Chemistry A, 2015, vol. 3, # 25, p. 13568 - 13576]

34
4-bromo-7-(5-(9-octyl-9H-carbazol-3-yl)thiophen-2-yl)benzo[c][1,2,5]thiadiazole [ No CAS ]
[ 267221-90-9 ]
C₁₀₈H₉₆N₁₀S₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
50.6%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; potassium carbonate; tris-(o-tolyl)phosphine In toluene at 80℃; for 24h; Inert atmosphere;

Reference： [1]Zhou, Pei; Dang, Dongfeng; Wang, Qiong; Duan, Xiongwei; Xiao, Manjun; Tao, Qiang; Tan, Hua; Yang, Renqiang; Zhu, Weiguo [Journal of Materials Chemistry A, 2015, vol. 3, # 25, p. 13568 - 13576]

35
[ 1210390-72-9 ]
[ 267221-90-9 ]
C₁₁₄H₁₃₅N₇O₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
40%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In water; toluene at 90℃; for 48h; Inert atmosphere; Schlenk technique;

Reference： [1]Liu, Xin; Xie, Yuan; Zhao, Haobin; Cai, Xinyi; Wu, Hongbin; Su, Shi-Jian; Cao, Yong [New Journal of Chemistry, 2015, vol. 39, # 11, p. 8771 - 8779]

36
[ 267221-90-9 ]
[ 444579-39-9 ]
tris(4-(3-hexyl-5-(7-(4-hexylthiophen-2-yl)benzo[c][1,2,5]thiadiazol-4-yl)thiophen-2-yl)phenyl)amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In water; toluene

Reference： [1]Liu, Cheng-Fang; Jiu, Yuanda; Wang, Jianyun; Yi, Jianpeng; Zhang, Xin-Wen; Lai, Wen-Yong; Huang, Wei [Macromolecules, 2016, vol. 49, # 7, p. 2549 - 2558]

37
3-bromo-9-hexadecyl-6-(thiophen-2-yl)-9H-carbazole [ No CAS ]
[ 267221-90-9 ]
tris{4-[9-hexadecyl-6-(thiophen-2-yl)-9H-carbazol-3-yl]phenyl}amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
40%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; tetrabutylammomium bromide; potassium carbonate In water; toluene for 92h; Inert atmosphere; Reflux;	General procedure for the preparation of Ia/Ib, IIa/IIb and III General procedure: Tris(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amine (0.10g, 0.16mmol) and corresponding aryl halide (3a, 3b or 3-Iodo-9H-carbazole) (4,5 eq.) were dissolved in solvent mixture of toluene (20mL) and H2O (5mL). Powdered anhydrous potassium carbonate (1.4g, 100mmol) and tetrabutylammonium bromide (10mg, 0.03mmol) were added and the reaction mixture was purged with nitrogen for 10 min and degassed. Next tetrakis(triphenylphosphine)palladium(0) (18mg, 0.016mmol) was added to the reaction mixture. The reaction mixture was refluxed for 92h under nitrogen, cooled to r.t. and poured onto water (50mL). The resulting mixture was extracted with CH2Cl2 (4×20mL) and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure and the residue was purified by column chromatography (n-hexane: toluene 3:1 v/v for Ib and Ia, n-hexane: CH2Cl2 5:3 v/v for IIa, n-hexane: CH2Cl2 2:1 v/v for IIb and n-hexane: CH2Cl2 1:1 v/v and CH2Cl2 for III were used as eluents).