[ CAS No. 193978-23-3 ]

Name: 193978-23-3|4,4,5,5-Tetramethyl-2-(2-thienyl)-1,3,2-dioxaborolane|97%
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Quality Control of [ 193978-23-3 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

Alternatived Products of [ 193978-23-3 ]

Product Details of [ 193978-23-3 ]

CAS No. :	193978-23-3	MDL No. :	MFCD05663878
Formula :	C₁₀H₁₅BO₂S	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	FFZHICFAHSDFKZ-UHFFFAOYSA-N
M.W :	210.10	Pubchem ID :	10703628
Synonyms :

Calculated chemistry of [ 193978-23-3 ]

Physicochemical Properties

Num. heavy atoms :	14
Num. arom. heavy atoms :	5
Fraction Csp3 :	0.6
Num. rotatable bonds :	1
Num. H-bond acceptors :	2.0
Num. H-bond donors :	0.0
Molar Refractivity :	60.8
TPSA :	46.7 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	Yes
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.72 cm/s

Lipophilicity

Log Po/w (iLOGP) :	0.0
Log Po/w (XLOGP3) :	2.62
Log Po/w (WLOGP) :	2.05
Log Po/w (MLOGP) :	1.22
Log Po/w (SILICOS-IT) :	2.5
Consensus Log Po/w :	1.68

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	0.0
Bioavailability Score :	0.55

Water Solubility

Log S (ESOL) :	-2.99
Solubility :	0.214 mg/ml ; 0.00102 mol/l
Class :	Soluble
Log S (Ali) :	-3.25
Solubility :	0.118 mg/ml ; 0.000561 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-3.27
Solubility :	0.112 mg/ml ; 0.000535 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	3.18

Safety of [ 193978-23-3 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 193978-23-3 ]

* 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.

Upstream synthesis route of [ 193978-23-3 ]
Downstream synthetic route of [ 193978-23-3 ]

[ 193978-23-3 ] Synthesis Path-Upstream 1~5

1
[ 589-87-7 ]
[ 193978-23-3 ]
[ 40133-22-0 ]

Yield	Reaction Conditions	Operation in experiment
74.6%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In tetrahydrofuran; water; toluene for 5 h; Reflux	A mixture of 1-bromo-4-iodobenzene (2.0 g, 7.07 mmol), 4,4,5,5-tetramethyl-2-(thiophen-2-yl)-1,3,2-dioxaborolane (2.97 g, 14.1 mmol), Pd(PPh34 (408 mg, 0.35 mmol), and Na2CO3 (1.49 g, 14.1 mmol) were dissolved in toluene (40 mL), THF (15 mL), and H2O (15 mL) and the reaction mixture was refluxed for 5 h. After completion of the reaction (indicated by TLC), the solvent was removed under vacuum, H2O (30 mL) and CH2Cl2 (40 mL) were added. The organic layer was separated and dried on anhydrous MgSO4. The solvent was removed under reduced pressure. Then the crude product was purified by flash column chromatography on silica gel to give 2-(4-bromophenyl) thiophene (1.26 g, 74.6percent). Spectral data matched well with values reported in the literature.27 1HNMR (400 MHz, CDCl3: 7.48 (d, 3.6 Hz, 4 H), 7.29(d, 4.4 Hz, 2 H), 7.07 (dt, 1.4, 4.4 Hz, 1 H).

Reference： [1] Journal of Nanoscience and Nanotechnology, 2016, vol. 16, # 1, p. 910 - 919
[2] ChemPlusChem, 2017, vol. 82, # 5, p. 742 - 749

2
[ 15155-41-6 ]
[ 193978-23-3 ]
[ 165190-76-1 ]

Reference： [1] Journal of Polymer Science, Part A: Polymer Chemistry, 2011, vol. 49, # 15, p. 3355 - 3365
[2] Tetrahedron, 2013, vol. 69, # 44, p. 9175 - 9182

3
[ 188290-36-0 ]
[ 25015-63-8 ]
[ 193978-23-3 ]
[ 175361-81-6 ]

Yield	Reaction Conditions	Operation in experiment
45%	With (^iPrPNP)CoCH₂SiMe₃ In neat (no solvent) at 60℃; for 24 h;	EXAMPLE 9 - Borylation of Aromatic Five-Membered Heterocycle According to the reaction scheme illustrated in Figure 2(a), a scintillation vial (with a magnetic stir bar) was charged with cobalt complex (0.01 mmol) selected from 1-4, 2 methylfuran (1 mmol) and pinacolborane (1 mmol). The reaction was monitored by the analysis of an aliquot of the mixture by GC-FID. The mixture was allowed to stir to completion at room temperature and was quenched by exposure to air. The resulting solid was solubilized in CDC1₃, 1 ] 3 passed through a plug of silica gel in a Pasteur pipette and then analyzed by H and C NMR spectroscopy without further purification. If desired, the foregoing reaction can also be administered in 2 ml of tetrahydrofuran (THF). Figure 2(a) provides conversion percentages for cobalt complexes 1-4 with values in parenthesis as isolated yields. Further, Figure 2(b) details additional borylation products achieved with Co complexes 2 and 3 according to the foregoing reaction parameters.

Reference： [1] Patent: WO2015/89119, 2015, A1, . Location in patent: Page/Page column 34

4
[ 188290-36-0 ]
[ 76-09-5 ]
[ 22092-92-8 ]
[ 193978-23-3 ]
[ 175361-81-6 ]

Yield	Reaction Conditions	Operation in experiment
39%	Stage #1: With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 1,3-dicyclohexyl-1H-imidazol-3-ium chloride; sodium t-butanolate In methyl cyclohexane at 110℃; for 4 h; Glovebox; Inert atmosphere Stage #2: at 20℃; for 1.5 h; Inert atmosphere	General procedure: In a glovebox filled with nitrogen, [Ir(OMe)(cod)]2 (33.1 mg, 0.050 mmol, 0.10 equiv), ICy·HCl(26.2 mg, 0.10 mmol, 0.20 equiv), NaOt-Bu (19.2 mg, 0.20 mmol, 0.40 equiv) andmethylcyclohexane (1.0 mL) were added to a 10 mL-sample vial with a Teflon-sealed screwcap, andstirred for 5 min at room temperature. A heteroarene (0.50 mmol, 1.0 equiv) and 1g (113.1 mg, 2.0equiv) were added, and then the cap was screwed on seal the vial. The vial was stirred at 110 °C for4 h. The reaction mixture was cooled to room temperature. Pinacol (236 mg, 2.0 mmol) in THF (2.0mL) was added and the reaction mixture was stirred under N2 at room temperature for 1.5 h. Thecrude mixture was filtered through a pad of Celite and eluted with EtOAc. The filtrate wasconcentrated in vacuo and sampled for analysis by 1HNMR spectroscopy using 1,2-dichloroethaneas an internal standard. The residue was purified by flash column chromatography over silica geleluting with hexane/EtOAc. Product-containing fractions were concentrated in vacuo to give a pureborylated product.

Reference： [1] Beilstein Journal of Organic Chemistry, 2016, vol. 12, p. 654 - 661

5
[ 188290-36-0 ]
[ 73183-34-3 ]
[ 193978-23-3 ]
[ 175361-81-6 ]

Reference： [1] Tetrahedron Letters, 2002, vol. 43, # 32, p. 5649 - 5651

[ 193978-23-3 ] Synthesis Path-Downstream 1~69

1
[ 188290-36-0 ]
[ 73183-34-3 ]
[ 193978-23-3 ]
[ 175361-81-6 ]

Reference： [1]Tetrahedron Letters,2002,vol. 43,p. 5649 - 5651

2
[ 188290-36-0 ]
[ 73183-34-3 ]
[ 193978-23-3 ]

Yield	Reaction Conditions	Operation in experiment
100%	With [Ir(COD)(OMe)]2-Covalent organic framework (4-iPr) at 100℃; for 24h; Inert atmosphere;
88%	In octane at 25℃; for 4h;	3 Example 3; Synthesis of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene Example 3 Synthesis of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene: The same procedure as Example 1 was repeated with the exception of using Ir(OMe)(COD) instead of IrCl(COD) for the catalyst, and allowing to react for 4 hours at 25°C. The yield was 88%.
86%	In octane at 25℃; for 4h;	4 Example 4; Synthesis of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene Example 4 Synthesis of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene: The same procedure as Example 1 was repeated with the exception of using Ir(OH)(COD) instead of IrCl(COD) for the catalyst and allowing to react for 4 hours at 25°C. The yield was 86%.

82%	In octane at 25℃; for 4h;	5 Example 5; Synthesis of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene Example 5 Synthesis of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene: The same procedure as Example 1 was repeated with the exception of using Ir(OPh)(COD) instead of IrCl(COD) for the catalyst and allowing to react for 4 hours at 25°C. The yield was 82%.
75%	In octane at 80℃; for 16h;	1 Example 1 Example 1 Bis(pinacolate)diboron (1 mmol), aromatic heterocyclic compound in the form of thiophene (10 mmol), catalyst in the form of IrCl (COD) (0.03 mmol), ligand in the form of dtbpy (0.03 mmol) and 6 ml of octane were mixed followed by stirring while heating for 16 hours at 80°C. After allowing to cool to room temperature, the mixture was diluted with toluene and washed with saturated saltwater. The organic layer was concentrated under reduced pressure followed by distilling off the residue to obtain 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiophene at a yield of 75%. 1H-NMR (400 MHz, CDCl3, TMS): δ 1.35 (s, 12H), 7.20 (dd, 1H, J = 3.7 and 4.6 Hz), 7.64 (d, 1H, J = 4.6 Hz), 7.66 (d, 1H, J = 3.4 Hz) 13C-NMR (100 MHz, CDCl3, TMS): δ 24.75, 84.07, 128.21, 132.35, 137.14 MS m/e: 43(33), 110(50), 111 (100) , 124(82), 195 (72) , 210(M+,96) Exact mass calculated for C10H15BO2S: 210.0886, found: 210.0881
60%	In octane at 80℃; for 16h;	2 Example 2; Synthesis of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene Example 2 Synthesis of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene: The same procedure as Example 1 was repeated with the exception of using bpy instead of dtbpy for the ligand. The yield was 60%.
57%	With 2-(2',4'-difluorophenyl)-5-(trifluoromethyl)pyridine In n-heptane at 80℃; for 72h; Inert atmosphere; Schlenk technique; Glovebox;
	With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 4,4'-di-tert-butylbipyridine In cyclohexane at 20℃;
	In cyclohexane (Schlenk, N2 atm.) the soln. in cyclohexane was stirred at room temp. overnight; column chromy. (1:1 ethyl acetate:hexane);
	With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 4,4'-di-tert-butyl-2,2'-bipyridine In hexane

Reference： [1]Wu, Xiaowei; Han, Xing; Liu, Yuhao; Liu, Yan; Cui, Yong [Journal of the American Chemical Society, 2018, vol. 140, # 47, p. 16124 - 16133]
[2]Current Patent Assignee: MITSUBISHI CHEMICAL HOLDINGS CORPORATION; Mitsubishi Chemical Corp (in: MCHC Group) - EP1481978, 2004, A1 Location in patent: Page 10
[3]Current Patent Assignee: MITSUBISHI CHEMICAL HOLDINGS CORPORATION; Mitsubishi Chemical Corp (in: MCHC Group) - EP1481978, 2004, A1 Location in patent: Page 10
[4]Current Patent Assignee: MITSUBISHI CHEMICAL HOLDINGS CORPORATION; Mitsubishi Chemical Corp (in: MCHC Group) - EP1481978, 2004, A1 Location in patent: Page 10-11
[5]Current Patent Assignee: MITSUBISHI CHEMICAL HOLDINGS CORPORATION; Mitsubishi Chemical Corp (in: MCHC Group) - EP1481978, 2004, A1 Location in patent: Page 9-10
[6]Current Patent Assignee: MITSUBISHI CHEMICAL HOLDINGS CORPORATION; Mitsubishi Chemical Corp (in: MCHC Group) - EP1481978, 2004, A1 Location in patent: Page 10
[7]Falivene, Laura; Wiedemann, Thomas; Göttker-Schnetmann, Inigo; Caporaso, Lucia; Cavallo, Luigi; Mecking, Stefan [Journal of the American Chemical Society, 2018, vol. 140, # 4, p. 1305 - 1312]
[8]Boller, Timothy M.; Murphy, Jaclyn M.; Hapke, Marko; Ishiyama, Tatsuo; Miyaura, Norio; Hartwig, John F. [Journal of the American Chemical Society, 2005, vol. 127, # 41, p. 14263 - 14278]
[9]Boller, Timothy M.; Murphy, Jaclyn M.; Hapke, Marko; Ishiyama, Tatsuo; Miyaura, Norio; Hartwig, John F. [Journal of the American Chemical Society, 2005, vol. 127, # 41, p. 14263 - 14278]
[10]Poh, Wei Church; Au-Yeung, Ho-Leung; Chan, Alan Kwun-Wa; Hong, Eugene Yau-Hin; Cheng, Yat-Hin; Leung, Ming-Yi; Lai, Shiu-Lun; Low, Kam-Hung; Yam, Vivian Wing-Wah [Chemistry - An Asian Journal, 2021, vol. 16, # 22, p. 3669 - 3676]

3
[ 188290-36-0 ]
[ 61676-62-8 ]
[ 193978-23-3 ]

Yield	Reaction Conditions	Operation in experiment
95%	Stage #1: thiophene With n-butyllithium In tetrahydrofuran at 20℃; for 0.5h; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at 20℃; for 0.333333h; Further stages.;
88%	Stage #1: thiophene With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; Schlenk technique; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; Schlenk technique;	4,4,5,5-Tetramethyl-2-(thiophen-2-yl)-1,3,2-dioxaborolane (5i) Following a modified literature procedure,30 n-BuLi (13.5 mL, 21.6mmol) was added dropwise to a solution of thiophene (2.0 g, 1.90 mL,23.8 mmol) in dry THF (50 mL) at -78 °C. The solution was stirred at r.t. for 1 h, then it was cooled again to -78 °C and 2-isopropoxy-4,4,5,5-tetramethydioxoborolane (5.2 g, 5.7 mL, 28.1 mmol) was added.The reaction mixture was stirred at r.t. for 16 h, then the solvent was removed under reduced pressure. The residue was taken up with H2O (30 mL) and the aq phase was extracted with Et2O (3 × 30 mL).The combined organic layers were dried over MgSO4 and concentratedin vacuo. The crude product was purified by chromatography onsilica gel (PE/EtOAc = 95:5) to give boronic ester 5i as a white solid(3.99 g, 88%). All analytical data matched that previously reported.31 1H NMR (400 MHz, CDCl3): δ = 7.65 (m, 2 H, thio-H), 7.20 (t, J = 4.4 Hz,1 H, thio-H), 1.35 (s, 12 H, 4 × C-CH3).
86%	Stage #1: thiophene With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at 20℃; for 0.5h;	2.2.1. Synthesis of 4,4,5,5-tetramethyl-2-(thiophen-2-yl)-1,3,2-dioxaborolane [22] n-BuLi (41.18 mL, 65.9 mmol, 1.6 M in hexane) was added dropwise to the stirred solution of thiophene (5.04 g, 59.9 mmol) in THF (50mL) at -78 °C and the solution was stirred for 30 min at room temperature. After cooling to-78 °C, 2-isopropoxy-4,4,5,5-tetramethyldioxoborolane (11.14 g, 59.9 mmol) in THF (80 mL) was added and the reaction mixture was allowed to stir for 30 min at room temperature. After completion of the reaction (indicated by TLC), solvent was removed under vacuum and the residue was taken up in CHCl3. An aqueous 5N HCl (50 mL) was added under vigorous stirring. The organic layer was collected and dried over MgSO4. After evaporation of the solvent the product was recrystallized from pentane (10.78 g, 86%). 1H NMR (400MHz, CDCl3): δ 7.65(d, 3.6Hz, 1H), 7.63 (d, 4.6Hz, 1H), 7.20 (dd, 4.7, 3.6Hz, 1H), 1.34 (s, 12H).

86%	Stage #1: thiophene With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h;	2.2.6. Synthesis of 4,4,5,5-Tetramethyl-2-(thiophen-2-yl)-1,3,2-Dioxaborolane n-BuLi (41.18 mL, 65.9 mmol, 1.6 M in hexane) was added drop wise to the stirred solution of thiophene (5.04 g,59.9 mmol) in 50 mL of THF at -78 °C. Then the solution was stirred for 30 min at room temperature. Aftercooling to -78 °C, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (11.14 g, 59.9 mmol) in 80 mL of THF was added and the reaction mixture was allowed to stirfor 30 min at room temperature. After completion of the reaction (indicated by TLC), solvent was removed under vacuum and the residue was taken up in CHCl3. Aqueous5 N HCl (50 mL) was added under vigorous stirring for30 min. The organic layer was collected and dried over MgSO4. After evaporation of the solvent the product was recrystallized from pentane (10.78 g, 86.0%). Spectral data matched well with values reported in the literature.26 1HNMR (400 MHz, CDCl3: 7.65(d, 3.6 Hz, 1 H), 7.63 (d,4.6 Hz, 1 H), 7.20 (dd, 4.7, 3.6 Hz, 1 H), 1.34 (s, 12 H).
81%	Stage #1: thiophene With n-butyllithium In tetrahydrofuran at -78℃; for 0.333333h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at 20℃; Inert atmosphere;
68%	Stage #1: thiophene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃; for 1h; Inert atmosphere;

Reference： [1]Dienes, Yvonne; Durben, Stefan; Karpati, Tamas; Neumann, Toni; Englert, Ulli; Nyulaszi, Laszlo; Baumgartner, Thomas [Chemistry - A European Journal, 2007, vol. 13, # 26, p. 7487 - 7500]
[2]Casoni, Giorgia; Myers, Eddie L.; Aggarwal, Varinder K. [Synthesis, 2016, vol. 48, # 19, p. 3241 - 3253]
[3]Jeon, Sang Kyu; Thirupathaiah, Bodakuntla; Kim, Choongik; Lim, Kwon Taek; Lee, Jun Yeob; Seo, Sungyong [Dyes and Pigments, 2015, vol. 114, # C, p. 146 - 150]
[4]Lee, Eunsoo; Thirupathaiah, Bodakuntla; Han, Jaeuk; Jung, Dahae; Kwon, Guhyun; Kim, Choongik; Seo, Sung Yong [Journal of Nanoscience and Nanotechnology, 2016, vol. 16, # 1, p. 910 - 919]
[5]Capan, Asli; Veisi, Hojat; Goren, Ahmet C.; Ozturk, Turan [Macromolecules, 2012, vol. 45, # 20, p. 8228 - 8236]
[6]Mei, Qunbo; Tian, Ruqiang; Shi, Yujie; Hua, Qingfang; Chen, Chen; Tong, Bihai [New Journal of Chemistry, 2016, vol. 40, # 3, p. 2333 - 2342]

4
[ 1003-09-4 ]
[ 73183-34-3 ]
[ 193978-23-3 ]

Yield	Reaction Conditions	Operation in experiment
94%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In toluene at 80℃; for 24h; Inert atmosphere;
89%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In toluene for 24h; Reflux; Inert atmosphere; Schlenk technique;
85%	With potassium acetate; palladium diacetate; (1R,3S,5S,7R)-8-Cyclohexyl-1,3,5,7-tetramethyl-2,4,6-trioxa-8-phosphaadamantane In tetrahydrofuran at 70℃; for 12h; Inert atmosphere; Sealed tube;	General procedure for borylation at elevated temperatures (B). General procedure: An oven-dried ace pressure tube was evacuated and backfilled with argon. Pd(OAc)2 (0.005 - 0.02 mmol, 0.5 - 2 mol%) and ligand (0.0125 - 0.05 mmol, 1.25 - 5 mol%), were added and the tube was evacuated and backfilled with argon. THF (2.00 mL), aryl halide (1 mmol), bis(pinacolato)diboron (2 - 3 mmol), KOAc (3 mmol), and n-decane (0.5 mmol, internal standard), were added to the tube. The tube underwent a final evacuation/backfill cycle, sealed with a screw cap, and allowed to stir at 70 °C for the specified times (12 - 24 h). Conversion, selectivity and GC yield were quantified from an aliquot (0.20 mL) of the reaction mixture using GC-FID. Upon completion, the GC sample was transferred back into the main reaction mixture, an aqueous work-up was performed (EtOAc:H2O, 1:1). The organic layer was dried over MgSO4, filtered through a cotton wool plug and concentrated on a rotary evaporator. The isolated yield was obtained by purification of the crude product through column chromatography using silica gel (EtOAc-hexane).

83%	With copper(l) iodide; tributyl-amine; potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃;
73%	With C₅₄H₄₄NO₂PPdS; potassium acetate In 2-methyltetrahydrofuran at 90℃; for 24h; Inert atmosphere; Sealed tube;
72%	With potassium methanolate; [1,3-bis(2,4,6-trimethylphenyl)imidazol]-2-ylidene; zinc dibromide In tert-butyl methyl ether at 20℃; Green chemistry;
61%	With DPEPhos; sodium acetate; bis(dibenzylideneacetone)-palladium⁽⁰⁾ for 12h; Heating;
46%	With C₃₇H₅₁ClFeNPPd; potassium acetate In 1,4-dioxane at 80℃; for 3h; Inert atmosphere;
66 %Spectr.	With C₂₀H₂₈Cl₂CoFeNOP; potassium methanolate; methyllithium In tert-butyl methyl ether at 50℃; for 24h; Inert atmosphere; Schlenk technique; Sealed tube;

Reference： [1]Rodrigues, Carime V.; Johnson, Katherine R.; Lombardi, Vincent C.; Rodrigues, Marcelo O.; Sobrinho, Josiane A.; De Bettencourt-Dias, Ana [Journal of Medicinal Chemistry, 2021, vol. 64, # 11, p. 7724 - 7734]
[2]Johnson, Katherine R.; Lombardi, Vincent C.; de Bettencourt-Dias, Ana [Chemistry - A European Journal, 2020, vol. 26, # 52, p. 12060 - 12066]
[3]Lamola, Jairus L.; Moshapo, Paseka T.; Holzapfel, Cedric W.; Christopher Maumela, Munaka [Tetrahedron Letters, 2022, vol. 88]
[4]Kleeberg, Christian; Dang, Li; Lin, Zhenyang; Marder, Todd B. [Angewandte Chemie - International Edition, 2009, vol. 48, p. 5350 - 5354][Angew. Chem., Int. Ed., 2009, vol. 121, p. 5454 - 5458]
[5]Wang, Xin; Liu, Wei-Gang; Tung, Chen-Ho; Wu, Li-Zhu; Cong, Huan [Organic Letters, 2019, vol. 21, # 20, p. 8158 - 8163]
[6]Bose, Shubhankar Kumar; Marder, Todd B. [Organic Letters, 2014, vol. 16, # 17, p. 4562 - 4565]
[7]Dzhevakov, Pavel B.; Topchiy, Maxim A.; Zharkova, Daria A.; Morozov, Oleg S.; Asachenko, Andrey F.; Nechaev, Mikhail S. [Advanced Synthesis and Catalysis, 2016, vol. 358, # 6, p. 977 - 983]
[8]Location in patent: experimental part Wang, Lianhui; Li, Jingya; Cui, Xiuling; Wu, Yusheng; Zhu, Zhiwu; Wu, Yangjie [Advanced Synthesis and Catalysis, 2010, vol. 352, # 11-12, p. 2002 - 2010]
[9]Yao, Wubing; Fang, Huaquan; Peng, Sihan; Wen, Huanan; Zhang, Lei; Hu, Aiguo; Huang, Zheng [Organometallics, 2016, vol. 35, # 10, p. 1559 - 1564]

5
[ 1119260-64-8 ]
[ 193978-23-3 ]
[ 1205683-86-8 ]

Yield	Reaction Conditions	Operation in experiment
85%	With tetraethylammonium hydroxide In water; toluene at 90℃; for 14h;	2.b; 24 Compound 3 (200 mg, 0.13 mmol), thiophene-2-boronic acid pinacol ester 9 (64 mg, 0.30 mmol) and Pd(PPh3)4 (1 mg) were dissolved in degassed toluene (5 ml_). Tetraethylammonium hydroxide solution (20% wt. in water, 2 mL) was thoroughly degassed and added to the reaction mixture. The resulting solution was heated at 90 5C for 14 h and the product was extracted into toluene. The toluene solution was dried over Na2SO4 and filtered through a plug of silica. After the removal of toluene, the resulting residue was purified by size exclusion chromatography (Bio-Rad, Bio-Beads S-X1 , THF) and a yellow solid (160 mg, 85% yield) was obtained after precipitation from methanol.UV-vis: λmax, nm (ε, cm L mol"1) = 367 (1 .75 x 105). 1H NMR (500 MHz, 7.5 mM, CDCI3, 20 0C, δ): 0.83 (m, 12H, -CH3), 1.06 (br, 8H, -CH2-), 1 .26 (br, 40H, - CH2-), 2.30 (m, 8H, -CH2-), 7.21 (br t, 4H, HBC-H), 7.25 (m, 2H, thiophene-H), 7.43 (m, 2H, thiophene-H), 7.58 (m, 4H, thiophene-H and fluorene-H), 7.73 (d, J = 7 Hz, 2H, fluorene-H), 7.79-7.88 (m, 12H, fluorene-H and HBC-H), 8.02 (br s, 4H, HBC-H), 8.22 (br s, 4H, HBC-H). 13C NMR (125 MHz, 12 mM, CDCI3, 20 °C, δ): 153.6, 152.0, 151.8, 151 .0, 145.4, 140.636, 140.5, 139.2, 133.4, 128.8, 128.4, 128.2, 124.7, 124.6, 123.1 , 123.0, 121 .7, 121 .7, 120.4, 120.3, 120.2, 120.1 , 120.1 (3), 1 18.8, 1 18.4, 1 18.2, 92.6, 55.7, 55.5, 40.6, 40.4, 31.9, 30.3, 30.2, 29.6, 29.5 (2), 29.4, 24.3, 22.7 (2), 14.2, 14.1. FT-IR (neat, cm"1): 3070, 2952, 2923, 2852, 1616, 1466, 1456, 1380, 1250, 989, 812, 759, 740, 692. MS-MALDI (m/z): M+ 1462.6. Elemental analysis: calcd. for C108H102S2, C 88.60, H 7.02, S 4.38; found C 86.6, H 7.2. Note: The elemental analysis indicates impurities in the sample and this is thought to be the mono-substituted derivative which can be observed in the MALDI mass spectrum of the sample. Efforts to purify the product by various chromatography techniques including HPLC and recycling GPC were unsuccessful.
85%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; tetraethylammonium hydroxide In toluene at 90℃; for 14h; Inert atmosphere;
85%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; tetraethylammonium hydroxide In water; toluene at 90℃; for 14h;

Reference： [1]Current Patent Assignee: UNIVERSITÄT ULM; UNIVERSITY OF MELBOURNE - WO2010/60160, 2010, A1 Location in patent: Page/Page column 13; 42-43
[2]Location in patent: scheme or table Wong, Wallace W. H.; Ma, Chang-Qi; Pisula, Wojciech; Mavrinskiy, Alexey; Feng, Xinliang; Seyler, Helga; Jones, David J.; Muellen, Klaus; Baeuerle, Peter; Holmes, Andrew B. [Chemistry - A European Journal, 2011, vol. 17, # 20, p. 5549 - 5560]
[3]Location in patent: scheme or table Wong, Wallace W.H.; Ma, Chang-Qi; Pisula, Wojciech; Yan, Chao; Feng, Xinliang; Jones, David J.; Muellen, Klaus; Janssen, Rene A.J.; Baeuerle, Peter; Holmes, Andrew B. [Chemistry of Materials, 2010, vol. 22, # 2, p. 457 - 466]

6
[ 1331748-13-0 ]
[ 193978-23-3 ]
[ 1331748-14-1 ]

Yield	Reaction Conditions	Operation in experiment
93%	With potassium carbonate In methanol; toluene at 80℃; for 0.166667h; Microwave irradiation;	9 Product 3 (0.052g, 0.105mmol), 2-Thiopheneboronic acid pinacole ester (0.066g, 0.314 mmol), K2CO3 (0.087g, 0.630 mmol) and PEPPSI-IPr (0.001 g, 0.0014mmol) were added to degassed toluene/methanol (1 :1 , 1 ml_) and microwave irradiated for 10 min at 80 °C. The solution was filtered and diluted with ethylacetate before it was washed with HCI (1 M, aq), brine, and H20. Flush chromatography gave the product in 93% yield (0.049 g).

Reference： [1]Current Patent Assignee: OBOE IPR; CELLUMINOVA - WO2011/102789, 2011, A1 Location in patent: Page/Page column 52-53

7
[ 19063-55-9 ]
[ 193978-23-3 ]
[ 1334143-26-8 ]

Reference： [1]Journal of Medicinal Chemistry,2011,vol. 54,p. 7055 - 7065

8
[ 62968-37-0 ]
[ 193978-23-3 ]
[ 1351934-01-4 ]

Yield	Reaction Conditions	Operation in experiment
96%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate; lithium hydroxide; In 1,4-dioxane; water; at 80℃; for 0.5h;Inert atmosphere;	General procedure: To a solution of 2-chloroheteroaryl compound 1 (0.50 mmol) in 1,4-dioxane (4.0 mL) were added pinacol boronate 3, 5, or 7 (0.60 mmol), Pd(OAc)2 (1.1 mg, 5.0 mumol), S-Phos (4.1 mg, 10.0 mumol), and 2 M LiOH solution (1.0 mL, 2.0 mmol) at room temperature, and the mixture was stirred for 30 min at 80 C under N2 atmosphere. The reaction was quenched by adding water, and then the mixture was extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. After filtration, the solvent was removed in vacuo, and the residue was purified by silica-gel column chromatography. The solvent was removed in vacuo, and the residue was triturated with Et2O to give biaryl compounds.

Reference： [1]Tetrahedron,2012,vol. 68,p. 272 - 279

9
[ 3141-27-3 ]
[ 193978-23-3 ]
[ 1081-34-1 ]

Reference： [1]Advanced Functional Materials,2011,vol. 21,p. 897 - 910

10
[ 1003-09-4 ]
[ 61676-62-8 ]
[ 193978-23-3 ]

Yield	Reaction Conditions	Operation in experiment
82%	Stage #1: 2-bromothiophene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃; Stage #3: With methanol In tetrahydrofuran; hexane	3.2 1-Hexyl-2-(4-(2-thiophenyl)phenyl)acetylene (1a) General procedure: n-BuLi in hexane (1.6 M, 65 mL, 0.10 mol) was slowly added toa solution of 2-bromothiophene (11 g, 0.068 mol) in THF (200 mL) at 78 C. After stirring for 2 h at this temperature, the mixturewas added to a solution of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (13 g, 0.068 mol) in 150 mL of THF. The mixture was warmed to room temperature and stirred overnight. The reactionwas terminated by adding a small amount of methanol and the resultant solution was washed with water three times. The solution was dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (eluent: hexane) to give 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)thiophene (11.7 g, 0.056 mol, 82%).
78%	With n-butyllithium In tetrahydrofuran; hexane at -60℃; Flow reactor;
	Stage #1: 2-bromothiophene With n-butyllithium at -78℃; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Reference： [1]Muroga, Tatsuoki; Sakaguchi, Toshikazu; Hashimoto, Tamotsu [Polymer, 2012, vol. 53, # 20, p. 4380 - 4387]
[2]Newby, James A.; Huck, Lena; Blaylock, D. Wayne; Witt, Paul M.; Ley, Steven V.; Browne, Duncan L. [Chemistry - A European Journal, 2014, vol. 20, # 1, p. 263 - 271]
[3]Location in patent: scheme or table Lo, Chih-Nan; Hsu, Chain-Shu [Journal of Polymer Science, Part A: Polymer Chemistry, 2011, vol. 49, # 15, p. 3355 - 3365]

11
[ 15155-41-6 ]
[ 193978-23-3 ]
[ 165190-76-1 ]

Reference： [1]Journal of Polymer Science, Part A: Polymer Chemistry,2011,vol. 49,p. 3355 - 3365
[2]Tetrahedron,2013,vol. 69,p. 9175 - 9182

12
[ 4316-58-9 ]
[ 193978-23-3 ]
[ 142807-63-4 ]

Yield	Reaction Conditions	Operation in experiment
86%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-ortho-cresyl phosphate; Aliquat 336; potassium carbonate In toluene at 85℃; for 48h; Inert atmosphere;	5 Synthesis of tris(4-(thiophen-2-yl)phenyl)amine (Formula 9) Anhydrous toluene (20 ml) as a solvent was placed in a 100 ml flask equipped with a magnetic stirring bar and a condenser, and then tris(4-bromophenyl)amine (1.0 g, 2.1 mmol) (Formula 7), 4,4,5,5-tetramethyl-2-(thiophen-2-yl)-1,3,2-dioxaborolane (1.7 g, 7.88 mmol) (Formula 8), dipalladiumtris(dibenzylacetone) (Pd2(dba)3) (0.1 g, 0.11 mmol), tri-o-tolyl phosphate (P(o-tolyl)3) (0.2 g, 0.4 mmol), potassium carbonate (K2CO3) (1.1 g, 8.3 mmol) and trioctylmethylammonium chloride (Aliquat 336) (1 drop) were added thereto. After oxygen was removed from the flask by vacuum-nitrogen cycling, the mixture was stirred at reflux under a nitrogen atmosphere at 85° C. for 48 hr. The stirring was stopped, and the toluene layer was collected, filtered through a short column (eluent=chloroform), and dried. The residue was purified by column chromatography (eluent=dichloromethane/hexane (1:1)) to afford 0.88 g (yield=86%) of tris(4-(thiophen-2-yl)phenyl)amine (Formula 9). 1H-NMR (CDCl3, δ ppm) 7.07 (dd, 3H, aromatic proton), 7.13 (d, 6H, aromatic proton), 7.24 (m, 6H, aromatic proton), 7.52 (d, 6H, aromatic proton)
57%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In 1,4-dioxane; water at 100℃; for 18h; Inert atmosphere;
	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In 1,2-dimethoxyethane; water at 85℃; Inert atmosphere;

Reference： [1]Current Patent Assignee: KOREA INSTITUTE OF SCIENCE AND TECHNOLOGY - US2013/234075, 2013, A1 Location in patent: Paragraph 0036
[2]Adelizzi, Beatrice; Rösch, Andreas T.; van Rijen, Daan J.; Martire, R. Simone; Esiner, Serkan; Lutz, Martin; Palmans, Anja R. A.; Meijer [Helvetica Chimica Acta, 2019, vol. 102, # 5]
[3]Location in patent: scheme or table Kearns, Jeremy T.; Roberts, Mark E. [Journal of Materials Chemistry, 2012, vol. 22, # 6, p. 2392 - 2394]

13
[ 193978-23-3 ]
[ 252011-38-4 ]
[ 1400773-58-1 ]

Yield	Reaction Conditions	Operation in experiment
65%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In 1,2-dimethoxyethane; ethanol; water at 80℃;	3.1 Monomer synthesis General procedure: 1-Hexyl-2-(4-bromophenyl)acetylene (7.0 g, 0.026 mol), 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)thiophene (5.4 g, 0.026 mol), dimethoxyethane (200 mL), ethanol (95 mL), Na2CO3aq (2.0 M, 95 mL), tetrakis(triphenylphosphine)palladium (0.60 g, 0.48 mmol) were placed in three-necked flask, and the mixture was stirred at 80 °C overnight. Ether (ca. 200 mL) was added, and the mixture was washed with water. Ether was evaporated, and the crude product was purified by silica gel column chromatography (eluent: hexane) to give 1-hexyl-2-[4-(2-thiophenyl)phenyl]acetylene (1a) (4.5 g, 0.017 mol, 65%). 1H NMR (CDCl3, ppm): 7.53-7.06 (m, 7H, Ar), 2.41 (t, J = 6.0 Hz, 2H, C≡C-CH2-), 1.61-1.30 (m, 8H, C≡C-CH2-(CH2)4-CH3), 0.90 (t, J = 7.0 Hz, 3H, CH3). 13C NMR (CDCl3, ppm): 143.8, 133.4, 128.1, 127.7, 125.5, 123.0, 91.5, 80.3, 31.4, 28.7, 28.6, 22.7, 19.5, 14.1. Anal. Calcd for C18H20S: C, 80.54; H, 7.51; S, 11.95. Found: C, 78.09; H, 8.28.

Reference： [1]Muroga, Tatsuoki; Sakaguchi, Toshikazu; Hashimoto, Tamotsu [Polymer, 2012, vol. 53, # 20, p. 4380 - 4387]

14
[ 1131148-99-6 ]
[ 193978-23-3 ]
[ 1400773-70-7 ]

Yield	Reaction Conditions	Operation in experiment
68%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In 1,2-dimethoxyethane; ethanol; water at 80℃;	3.14 1-(9,9-Dimethy)-2-fluorenyl)-2-[4-(2-thiophenyl)phenyl] General procedure: 1-Hexyl-2-(4-bromophenyl)acetylene (7.0 g, 0.026 mol), 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)thiophene (5.4 g, 0.026 mol), dimethoxyethane (200 mL), ethanol (95 mL), Na2CO3aq (2.0 M, 95 mL), tetrakis(triphenylphosphine)palladium (0.60 g, 0.48 mmol) were placed in three-necked flask, and the mixture was stirred at 80 °C overnight. Ether (ca. 200 mL) was added, and the mixture was washed with water. Ether was evaporated, and the crude product was purified by silica gel column chromatography (eluent: hexane) to give 1-hexyl-2-[4-(2-thiophenyl)phenyl]acetylene (1a)

Reference： [1]Muroga, Tatsuoki; Sakaguchi, Toshikazu; Hashimoto, Tamotsu [Polymer, 2012, vol. 53, # 20, p. 4380 - 4387]

15
[ 1028203-88-4 ]
[ 193978-23-3 ]
[ 1400773-62-7 ]

Yield	Reaction Conditions	Operation in experiment
76%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In 1,2-dimethoxyethane; ethanol; water at 80℃;	3.5 1-(4-Trimethylsilylphenyl)-2-[4-(2-thiophenyl)phenyl] General procedure: 1-Hexyl-2-(4-bromophenyl)acetylene (7.0 g, 0.026 mol), 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)thiophene (5.4 g, 0.026 mol), dimethoxyethane (200 mL), ethanol (95 mL), Na2CO3aq (2.0 M, 95 mL), tetrakis(triphenylphosphine)palladium (0.60 g, 0.48 mmol) were placed in three-necked flask, and the mixture was stirred at 80 °C overnight. Ether (ca. 200 mL) was added, and the mixture was washed with water. Ether was evaporated, and the crude product was purified by silica gel column chromatography (eluent: hexane) to give 1-hexyl-2-[4-(2-thiophenyl)phenyl]acetylene (1a)

Reference： [1]Muroga, Tatsuoki; Sakaguchi, Toshikazu; Hashimoto, Tamotsu [Polymer, 2012, vol. 53, # 20, p. 4380 - 4387]

16
[ 62856-18-2 ]
[ 193978-23-3 ]
[ 1400773-66-1 ]

Yield	Reaction Conditions	Operation in experiment
75%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In 1,2-dimethoxyethane; ethanol; water at 80℃;	3.9 1-(4-n-Octylphenyl)-2-[4-(2-thiophenyl)phenyl]acetylene General procedure: 1-Hexyl-2-(4-bromophenyl)acetylene (7.0 g, 0.026 mol), 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)thiophene (5.4 g, 0.026 mol), dimethoxyethane (200 mL), ethanol (95 mL), Na2CO3aq (2.0 M, 95 mL), tetrakis(triphenylphosphine)palladium (0.60 g, 0.48 mmol) were placed in three-necked flask, and the mixture was stirred at 80 °C overnight. Ether (ca. 200 mL) was added, and the mixture was washed with water. Ether was evaporated, and the crude product was purified by silica gel column chromatography (eluent: hexane) to give 1-hexyl-2-[4-(2-thiophenyl)phenyl]acetylene (1a)

Reference： [1]Muroga, Tatsuoki; Sakaguchi, Toshikazu; Hashimoto, Tamotsu [Polymer, 2012, vol. 53, # 20, p. 4380 - 4387]

17
[ 193978-23-3 ]
[ 852054-42-3 ]
[ 879480-38-3 ]

Reference： [1]Organic Letters,2013,vol. 15,p. 1028 - 1031

18
[ 188290-36-0 ]
[ 76-09-5 ]
[ 5419-55-6 ]
[ 193978-23-3 ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: thiophene With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: Triisopropyl borate In tetrahydrofuran at -78 - 20℃; for 2.5h; Inert atmosphere; Stage #3: 2,3-dimethyl-2,3-butane diol In tetrahydrofuran for 0.5h; Inert atmosphere;	1 General procedure for the synthesis of boronic ester General procedure: Under Ar, a stirred solution of thiophenic compound (30 mmol) in distilledTHF (100 mL) is cooled to 78 C. A 2.5 M solution of butyllithium(12 mL, 1 equiv) is added dropwise and the solution is stirred at thistemperature during 1 h. Triisopropylborate (21 mL, 3 equiv) isadded and the reaction mixture is allowed to warm to room temperature.After 2.5 h, a solution of pinacol (10.6 g) in THF (30 mL)was added. The reaction is stirred during 30 min and then thesolvent was removed in vacuo. The residue dissolved in diethylether is washed twice with water and dried over magnesium sulfate.The solvent is removed in vacuo. The product is used withoutfurther purification. 4.2.1.1. 4,4,5,5-Tetramethyl-2-thiophen-2-yl-1,3,2-dioxaboro-lane.This compound was prepared by the general procedure for thesynthesis of boronic ester, starting with 30mmol of thiophene. Yield:5.3 g, 85%.White powder.1HNMR(CDCl3): 1.36 (s,12H, CH3); 7.20 (dd,1H, 3.6, and 4.8 Hz); 7.64 (d,1H, 4.8 Hz); 7.66 (d,1H, 3.6 Hz). 13CNMR(CDCl3): 24.8 (CH3); 84.1; 128.2; 132.4; 137.2. MS (M): 210.

Reference： [1]Trippé-Allard, Gaëlle; Lacroix, Jean-Christophe [Tetrahedron, 2013, vol. 69, # 2, p. 861 - 866]

19
[ 1197992-32-7 ]
[ 193978-23-3 ]
[ 1189743-36-9 ]

Reference： [1]Organic and Biomolecular Chemistry,2013,vol. 11,p. 7011 - 7015

20
[ 25462-61-7 ]
[ 193978-23-3 ]
2,5-bis(2-thienyl)-1,4-phenylenediamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
59%	With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In ethanol; water; toluene; at 80℃;Inert atmosphere; Schlenk technique;	Synthesis of 2,S-bis(2-thienyl)-1,4-phenylenediamine (8). In a Schlenk flask, 2,5- dibromo-1,4-phenylenediamine (500 mg, 1.88 mmol) and thiophene-2-boronic acid pinacol ester 7 (1.58 g, 7.52 mmol) were charged under the protection ofnitrogen. After adding 30 ml toluene, 10 ml ethanol and 10 ml Cs2CO3 aqueous solution (2.0 mol/l), the mixture was degassed for 30 mi Pd(PPh3)4 (218 mg, 0.188 mmol) was added. The mixture was then heated to 80 C, stirred overnight, poured into brine and extracted with dichioromethane for several times. The organic phase was dried over Mg2504 and the solvent was evaporated in vacuo. The product was purified by chromatography on silica gel (CH2CI2) to give product 8 as yellow flaky crystal (310 mg, 59%). 1H NMR (400 MHz, CDCI3, ppm): 3.81 (br,4H), 6.82 (s, 2H), 7.12 (dd, i = 5.14, 3.53 Hz, 2H), 7.24 (dd, J = 3.27, 0.78 Hz, 2H),7.34 (dd, J 5.15, 1.01 Hz, 2H). m/z[M+H] calcd for C14H13N2S2 273.0521; HR-ESI observed 273.0515.

Reference： [1]Organic Letters,2013,vol. 15,p. 5714 - 5717
[2]Patent: WO2015/43722,2015,A1 .Location in patent: Page/Page column 75; 76

21
[ 1260685-63-9 ]
[ 193978-23-3 ]
3,6-bis([2,2'-bithiophen]-5-yl)-2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione [ No CAS ]

Reference： [1]Chemistry of Materials,2013,vol. 25,p. 4290 - 4296

22
[ 654676-12-7 ]
[ 193978-23-3 ]
[ 1519104-46-1 ]

Reference： [1]Journal of Organic Chemistry,2014,vol. 79,p. 618 - 629

23
[ 188290-36-0 ]
[ 25015-63-8 ]
[ 193978-23-3 ]
[ 175361-81-6 ]

Yield	Reaction Conditions	Operation in experiment
55%; 45%	With (iPrPNP)CoCH2SiMe3; In neat (no solvent); at 60℃; for 24h;	EXAMPLE 9 - Borylation of Aromatic Five-Membered Heterocycle According to the reaction scheme illustrated in Figure 2(a), a scintillation vial (with a magnetic stir bar) was charged with cobalt complex (0.01 mmol) selected from 1-4, 2 methylfuran (1 mmol) and pinacolborane (1 mmol). The reaction was monitored by the analysis of an aliquot of the mixture by GC-FID. The mixture was allowed to stir to completion at room temperature and was quenched by exposure to air. The resulting solid was solubilized in CDC13, 1 ] 3 passed through a plug of silica gel in a Pasteur pipette and then analyzed by H and C NMR spectroscopy without further purification. If desired, the foregoing reaction can also be administered in 2 ml of tetrahydrofuran (THF). Figure 2(a) provides conversion percentages for cobalt complexes 1-4 with values in parenthesis as isolated yields. Further, Figure 2(b) details additional borylation products achieved with Co complexes 2 and 3 according to the foregoing reaction parameters.

Reference： [1]Patent: WO2015/89119,2015,A1 .Location in patent: Page/Page column 34

24
[ 1116-98-9 ]
C₂₂H₁₈INO₄ [ No CAS ]
[ 193978-23-3 ]
[ 852054-42-3 ]
C₄₀H₃₄N₂O₈S₂ [ No CAS ]