Name: 591-50-4|Iodobenzene|98%
Brand: Ambeed
SKU: A272695
Price: 5.0 USD
Availability: InStock
Rating: 90 (22 reviews)

1
[ 110-86-1 ]
[ 591-50-4 ]
[ 94-36-0 ]
[ 1591-31-7 ]
[ 2113-51-1 ]
[ 20442-79-9 ]

Reference： [1]Journal of the American Chemical Society,1954,vol. 76,p. 445,446

2
[ 591-50-4 ]
[ 7579-20-6 ]
[ 64021-70-1 ]

Reference： [1]Journal of Organic Chemistry,1949,vol. 14,p. 97,101

3
[ 5093-70-9 ]
[ 591-50-4 ]
[ 3044-71-1 ]

Reference： [1]Tetrahedron,1993,vol. 49,p. 9713 - 9720

4
[ 591-50-4 ]
[ 1001-26-9 ]
[ 116519-41-6 ]

Reference： [1]Heterocycles,1988,vol. 27,p. 257 - 260
[2]Heterocycles,1988,vol. 27,p. 257 - 260

5
[ 591-50-4 ]
[ 626-44-8 ]
[ 612-71-5 ]

Reference： [1]Chemical and pharmaceutical bulletin,1983,vol. 31,p. 2313 - 2320

6
[ 591-50-4 ]
[ 201230-82-2 ]
[ 367-34-0 ]
N-(2,4,5-Trifluoro-phenyl)-benzamide [ No CAS ]

Reference： [1]Journal of Organic Chemistry,1992,vol. 57,p. 6351 - 6354

7
[ 1483-72-3 ]
[ 591-50-4 ]
[ 92-52-4 ]
[ 1591-31-7 ]
[ 2113-51-1 ]
[ 20442-79-9 ]
[ 108-90-7 ]

Reference： [1]Journal of Organic Chemistry,1990,vol. 55,p. 639 - 647

8
[ 66003-76-7 ]
[ 591-50-4 ]
[ 92-52-4 ]
[ 2051-60-7 ]
[ 1591-31-7 ]
[ 2113-51-1 ]
[ 20442-79-9 ]

Reference： [1]Journal of Organic Chemistry,1990,vol. 55,p. 639 - 647

9
[ 139-02-6 ]
[ 81447-67-8 ]
[ 101-84-8 ]
[ 591-50-4 ]
[ 625-95-6 ]
[ 3586-14-9 ]

Reference： [1]Journal of the American Chemical Society,1982,vol. 104,p. 3917 - 3923

10
[ 58377-39-2 ]
[ 591-50-4 ]
[ 1625-91-8 ]

Reference： [1]Chemistry Letters,1983,p. 1165 - 1166

11
[ 67765-96-2 ]
[ 7135-31-1 ]
[ 591-50-4 ]
[ 16863-96-0 ]

Reference： [1]Chemistry of Heterocyclic Compounds,1981,vol. 17,p. 1088 - 1090
Khimiya Geterotsiklicheskikh Soedinenii,1981,vol. 17,p. 1494 - 1496

12
[ 591-50-4 ]
[ 116632-40-7 ]
[ 19482-23-6 ]

Reference： [1]Journal of the Chemical Society,1962,p. 3784 - 3796

13
[ 1632-83-3 ]
[ 591-50-4 ]
[ 2622-63-1 ]

Yield	Reaction Conditions	Operation in experiment
97%	With 10 molpercent nickel based 2,5-dihydroxyterephthalic acid metal organic framework-74; In diethylene glycol dimethyl ether; at 160℃; for 18h;Sealed tube;	General procedure: In a typical experiment, a predetermined amount of Ni-MOF-74 was added to the 8 mL vial containing a mixture of iodobenzene (0.1030 g, 0.5 mmol), benzothiazole (0.1379 g, 1.0 mmol), Li2CO3 or KCl (1.0 mmol), and diphenyl ether (0.085 g, 0.5 mmol) as standard. 1-Methoxy-2-(2-methoxyethoxy)ethane (diglyme) (1 mL) was added and vial was tightly capped. Reaction mixture was heated at 160°C for 24 h. The catalyst loading was based on the molar ratio of nickel/iodobenzene. The reaction yield was monitored by withdrawing aliquots from the reaction mixture at different time intervals, diluting with ethylacetate (2 mL), quenching with an aqueous KOH solution (1percent, 1 mL), and then drying over anhydrous Na2SO4 before analyzing by GC with reference to diphenyl ether (internal equation with pure product), and further confirming product identity by GC?MS and NMR. To investigatethe recycle ability of Ni-MOF-74, the catalyst was filtered from the reaction mixture after the experiment, washed with ethylacetate, water, THF, and dried at 140°C under vacuum in 8 h. For the leaching test, a catalytic reaction was stopped after 12 h, analyzed by GC, and filtered to remove the solid catalyst. The reaction solution was then stirred for a further 12 h. Reaction progress, if any, was monitored by GC as previously described.
67%	With (1-(2-(tert-butylamino)ethyl)-3-mesityl-2,3-dihydro-1H-imidazol-2-yl)copper(I) iodide; lithium tert-butoxide; In N,N-dimethyl-formamide; at 140℃; for 8h;Glovebox;	General procedure: The product 12a is a representative reaction. To a vial (5 mL) containing caffeine (0.5 mmol), iodobenzene (1.0 mmol), catalyst 3e (0.05 mmol), and LiOtBu (1.0 mmol) was added DMF (1.0 mL) solvent under a glovebox atmosphere. After the substances were completely dissolved, the vial was screw-capped, taken outside the glovebox and heated at 140 °C for 8 h. The resulting mixture was filtered through Celite and washed with dichloromethane. The filtrate solution was concentrated in vacuo to afford the crude product, which was further purified by column chromatography using hexane/ethyl acetate as eluent to furnish 12a in 80percent yield.
46%	With potassium phosphate; Cu2(4,4?-biphenyldicarboxylate)2(4,4?-bipyridine); In Hexadecane; N,N-dimethyl-formamide; at 120℃; for 3h;Green chemistry;	General procedure: In a typical experiment, a pre-determined amount of Cu2(BPDC)2(BPY) was added to theflask containing a solution of iodobenzene (0.112 mL, 1 mmol),benzoxazole (0.238 g, 2 mmol), K3PO4(0.532 g, 2 mmol) and n-hexadecane (0.1 mL) as internal standard in DMF (4 mL). Thecatalyst concentration was calculated based on the molar ratio ofcopper/iodobenzene. The reaction mixture was stirred at 100Cunder an argon atmosphere for 180 min. The reaction conver-sion was monitored by withdrawing aliquots from the reactionmixture at different time intervals, quenching with an aqueousNaOH solution (5percent, 1 mL), drying over anhydrous Na2SO4, analyz-ing by GC with reference to n-hexadecane, and further confirmingproduct identity by GC?MS. To investigate the recyclability ofCu2(BPDC)2(BPY), the catalyst was filtered from the reaction mix-ture after the experiment, washed with copious amounts of DMF,dried under air at room temperature for 1 h, and reused if neces-sary. For the leaching test, a catalytic reaction was stopped after30 min, analyzed by GC, and filtered to remove the solid catalyst.The reaction solution was then stirred for a further 150 min. Reac-tion progress, if any, was monitored by GC as previously described.

Reference： [1]Angewandte Chemie - International Edition,2007,vol. 46,p. 7996 - 8000
[2]Journal of Molecular Catalysis A: Chemical,2017,vol. 426,p. 141 - 149
[3]Journal of Organic Chemistry,2011,vol. 76,p. 4741 - 4745
[4]Journal of the American Chemical Society,2007,vol. 129,p. 12404 - 12405
[5]Bulletin of the Chemical Society of Japan,1998,vol. 71,p. 467 - 473
[6]Tetrahedron Letters,2008,vol. 49,p. 1598 - 1600
[7]Advanced Synthesis and Catalysis,2017,vol. 359,p. 772 - 778
[8]Journal of Organometallic Chemistry,2014,vol. 761,p. 64 - 73
[9]Organic Letters,2004,vol. 6,p. 35 - 38
[10]Journal of Molecular Catalysis A: Chemical,2014,vol. 391,p. 74 - 82
[11]Organic Letters,2009,vol. 11,p. 1733 - 1736
[12]Chemistry - A European Journal,2011,vol. 17,p. 10113 - 10122
[13]RSC Advances,2014,vol. 4,p. 52307 - 52315

14
[ 591-50-4 ]
[ 188345-71-3 ]
N-(t-butyloxycarbonyl)-5-exo-phenyl-2-azabicyclo[2.2.1]heptane [ No CAS ]
N-(t-butyloxycarbonyl)-6-exo-phenyl-2-azabicyclo[2.2.1]heptane [ No CAS ]

Reference： [1]Tetrahedron,1999,vol. 55,p. 11879 - 11888

15
[ 591-50-4 ]
potassium <i>m</i>-cresolate [ No CAS ]
[ 3586-14-9 ]

Reference： [1]Journal of the American Chemical Society,1937,vol. 59,p. 2578

16
[ 591-50-4 ]
[ 108-39-4 ]
[ 3586-14-9 ]

Yield	Reaction Conditions	Operation in experiment
96%	With potassium carbonate; In N,N-dimethyl-formamide; at 110℃; for 3h;	General procedure: To prepare diaryl ethers using the Ullmann coupling reaction via O-arylation reactions, aryl halide (1 mmol), phenol derivative (1 mmol) and 0.2 g (1.5 mmol) of K2CO3 in DMF (5 mL) were placed into a round-bottom flask containing 0.05 g (0.02 mmol) of the catalyst. The above mixture was refluxed at 110 C for 3 h under vigorous stirring. When the reaction was complete, the reaction mixture was cooled and the solvent was removed under reduced pressure. Then, the mixture was diluted with CH2Cl2 and the catalyst was separated by an external magnet. The filtrate was evaporated on a rotary evaporator and the crude product was purified by column chromatography using ethyl acetate/n-hexane.
90%	With caesium carbonate; In tetrahydrofuran; at 150℃; for 3h;Inert atmosphere;Catalytic behavior;	General procedure: The catalytic O-arylation reactions were conducted in asealed stainless-steel reactor. A phenol (14 mmol), aryl halide(14 mmol), Cs2CO3 (14 mmol), tetrahydrofuran (THF, 10 mL),and the Cu2O/SiC catalyst (10 mg) were placed in the reactor.The reaction was performed under Ar at 150 C for 3 h. Afterthe reaction, the suspension was collected and centrifuged. Thesupernatant was analyzed using gas chromatography-massspectrometry (Bruker SCION SQ 456GC-MS, Germany). Theyields and TOFs were calculated based on the aryl halide usingthe following equations:Yield = Conversion (%) selectivity (%)= (1 - na/nb) x ntp/(ntp + nbp) x 100%TOF = Amount of aryl halides (mol) x conversion (%)x selectivity (%)/(mass of Cu2O/SiC (g) x Cu2O loading (%) xreaction time (h)/M[Cu2O] (g/mol))where na is the moles of aryl halide after reaction, nb is themoles of aryl halide before reaction, ntp is the moles of targetproduct after reaction, and nbp is the moles of byproduct afterreaction.
88%	With copper(l) iodide; 1-(dimethylamino-1-yl-pyridin-2-yl-methyl)naphthalen-2-ol; potassium carbonate; In dimethyl sulfoxide; at 120℃; for 24h;Green chemistry;Catalytic behavior;	General procedure: all reactions were carried out under air. Aryl halides (1.0 mmol) was treated with phenol (1.0 mmol) in the presence of 0.1 mmol CuI ,0.2 mmol 1-(alpha-aminobenzyl)-2-naphthols and 2.0 equiv K2CO3 in 3 mL DMSO at 120 for 24 h.The progress of the reaction was monitored by GC. After completion of the reaction, the catalyst was filtered easily and the product was extracted with EtOAc, The combined organic layers was dried over MgSO4 for 12 h. The solvent was evaporated under reduced pressure and the desired product purified by flash chromatography on a silica gel column using petroleum ether/ethyl acetate (10:1).

86%	With copper(II) glycinate monohydrate; potassium hydroxide; In dimethyl sulfoxide; at 80℃; for 8h;	General procedure: Experimental procedure for the synthesis of diaryl ether: To a stirred solution of iodo benzene (1.0 mmol) and phenol (1.0 mmol) in dry DMSO (2.0 ml) were added Cu catalyst 1 (0.02 mmol) and KOH (2.0 equiv) and the reaction mixture was heated at 80 C for 8 h. The progress of the reaction was monitored by TLC. After being cooled the reaction mixture at room temperature, the precipitated catalyst was separated by simple filtration and filtrate so obtained was diluted with ethyl acetate (10 ml). The organic layer was washed with water and dried over anhydrous Na2SO4. The solvent was evaporated under vacuum to give the crude product, which was purified by column chromatography with hexane as eluent to yield the expected product as yellowish oil. The products were analyzed by GC-MS, IR, 1H & 13C NMR analysis.
77%	With copper(I) oxide; caesium carbonate; In N,N-dimethyl-formamide; at 140℃; for 24h;Inert atmosphere; Green chemistry;	General procedure: In an oven-dried 50 mL round-bottomed flask with a condenser, phenol (1.0 mmol),bromobenzene (1.2 mmol), Cs2CO3 (1.0 mmol) and Cu2O/Cu-CNTs catalyst (0.06 g) were addedunder nitrogen atmosphere, followed by addition of DMSO (10 mL). The reaction mixture washeated in an oil bath at 140 and stirred at this temperature for 24 h. After the completion of thereaction (monitored by TLC), the reaction mixture was filtered. The filtrate was extracted withethyl acetate (3×10 mL) by adding a small amount of saturated aqueous NaCl solution. Theorganic layer was dried with anhydrous MgSO4 and concentrated to get the crude product. Theresulting residue was purified by column chromatography on silica gel to provide the desiredproduct.

Reference： [1]Research on Chemical Intermediates,2019,vol. 45,p. 2727 - 2747
[2]Advanced Synthesis and Catalysis,2008,vol. 350,p. 2205 - 2208
[3]Applied Organometallic Chemistry,2019,vol. 33
[4]Organic Letters,2003,vol. 5,p. 3799 - 3802
[5]Synlett,2012,p. 101 - 106
[6]Journal of Organic Chemistry,2009,vol. 74,p. 1971 - 1976
[7]Cuihua Xuebao/Chinese Journal of Catalysis,2017,vol. 38,p. 658 - 664
[8]Angewandte Chemie - International Edition,2016,vol. 55,p. 1704 - 1709
Angew. Chem.,2016,vol. 128,p. 1736 - 1741,5
[9]Synthetic Communications,2014,vol. 44,p. 2468 - 2477
[10]Tetrahedron Letters,2007,vol. 48,p. 8883 - 8887
[11]Tetrahedron Letters,2012,vol. 53,p. 4665 - 4668
[12]Journal of Organic Chemistry,2009,vol. 74,p. 3675 - 3679
[13]Organic Letters,2006,vol. 8,p. 5609 - 5612
[14]Applied Organometallic Chemistry,2017,vol. 31
[15]Tetrahedron Letters,2013,vol. 54,p. 6494 - 6497
[16]Journal of Molecular Catalysis A: Chemical,2012,vol. 357,p. 112 - 116
[17]Journal of Catalysis,2017,vol. 348,p. 146 - 150
[18]Tetrahedron Letters,2003,vol. 44,p. 3445 - 3446
[19]Applied Organometallic Chemistry,2012,vol. 26,p. 445 - 447
[20]Chemical Communications,2012,vol. 48,p. 3784 - 3786
[21]European Journal of Organic Chemistry,2008,p. 5112 - 5116
[22]RSC Advances,2014,vol. 4,p. 48362 - 48367
[23]ChemCatChem,2015,vol. 7,p. 3495 - 3502

17
[ 591-50-4 ]
[ 869-19-2 ]
N-(N-phenyl-glycyl)-(L)-leucine [ No CAS ]

Reference： [1]Tetrahedron Letters,2005,vol. 46,p. 2997 - 3001

18
[ 288-88-0 ]
[ 591-50-4 ]
[ 13423-60-4 ]

Yield	Reaction Conditions	Operation in experiment
96%	With potassium phosphate; copper(l) iodide; N,N`-dimethylethylenediamine; In N,N-dimethyl-formamide; at 110℃; for 72h;Inert atmosphere;	General procedure: A mixture of CuI (0.10 g, 0.50 mmol), the required azole(10 mmol), K3PO4 (4.4 g, 20 mmol), the required halide (12 mmol)and N,N0-dimethylethylenediamine (0.11 mL, 1.0 mmol) in DMF(5 mL) was degased and heated under argon at 110 C for 72 h.After filtration over celite (washing using AcOEt) and removal ofthe solvents, the crude product is purified by chromatography oversilica gel (the eluent is given in the product description). 4.3.1 1-Phenyl-1H-1,2,4-triazole (2a) Compound 2a was prepared from 1,2,4-triazole (0.69 g) and iodobenzene (1.4 mL) using the general procedure 1, and was isolated (eluent: heptane/AcOEt 7:3) in 96% yield as a yellow powder: mp 48 C (lit. 28 46 C); 1H NMR (CDCl3, 300 MHz) 7.42 (m, 1H), 7.53 (m, 2H), 7.71 (m, 2H), 8.15 (s, 1H), 8.74 (s, 1H); 13C NMR (CDCl3, 75 MHz) 120.1 (2CH), 128.3 (CH), 129.9 (2CH), 137.1 (C), 140.9 (CH), 152.7 (CH).
91%	With caesium carbonate;copper(I) oxide; trans-N,N'-bis(pyridin-2-ylmethylene)cyclohexane-1,2-diamine; In DMF (N,N-dimethyl-formamide); at 50 - 82℃; for 24 - 72h;Conversion of starting material;	Example 1.17 [0636] Preparation of 1-phenyl-1H-1,2,41 triazole [0637] Operating protocol A (82 C., 48 hours) was followed using 117 mg of Chxn-Py-Al (0.4 mmoles), 336 ?l of iodobenzene (3 mmoles), 138 mg of 1,2,4-triazole (2 mmoles), 1.042 g of caesium carbonate (3.2 mmoles) and 1.2 ml of DMF. [0638] The degree of transformation and selectivity were 100% and 98% respectively. [0639] The residue obtained following treatment was purified by silica gel chromatography (eluent: hexane/dichloromethane, 100/0 to 50/50). [0640] 264 mg of a dark yellow solid was obtained in a yield of 91%. [0641] Pale yellow needles were obtained after re-crystallisation from chloroform. [0642] The compound obtained had the following formula: [CHEMMOL-00056] [0643] The characteristics were as follows: [0644] MPt: 46 C. (CHCl3) (Lit: 46-47 C. given by Micetich, R G; Spevak, P; Hall, T W; Bains, B K; Heterocycles 1985, 23, 1645-1649); [0645] H NMR/CDCl3:? 8.52 (wide s, 1H, HI), 8.04 (wide s, 1H, H2), 7.53-7.65 (m, 2H, H4,8), 7.26-7.51 (m, 3H, H5,6,7); [0646] 13C NMR/CDCl3: ? 152.55 (C1), 140.88 (C2), 139.96 (C3), 129.73 (C5 and C7), 128.15 (C6), 119.99 (C4 and C8); [0647] GC/MS: Rt=14.02 min, M/Z=145, purity=100%; [0648] Rf=0.21 (eluent: dichloromethane/ethyl acetate, 90/10). Example 1.18 [0649] Preparation of 1-phenyl-1H-[1,2,4]triazole [0650] Operating protocol A (82 C., 24 hours) was followed using 117 mg of Chxn-Py-Al (0.4 mmoles), 336 ?l of iodobenzene (3 mmoles), 138 mg of 1,2,4-triazole (2 mmoles), 1.042 g of caesium carbonate (3.2 mmoles) and 1.2 ml of DMF. [0651] The degree of transformation and selectivity were 79% and 99% respectively. [CHEMMOL-00057] Example 1.19 [0652] Preparation of 1-phenyl-1H-[1,2,4]triazole Example 1.18 was repeated, operating at 50 C. (72 hours). The degree of transformation and selectivity for 1-phenyl-1H-[1,2,4-triazole] were 75% and 99% respectively. [0653] [CHEMMOL-00058]
91%		Operating protocol A (82 C., 48 hours) was followed using 117 mg of Chxn-Py-Al (0.4 mmoles), 336 mul of iodobenzene (3 mmoles), 138 mg of 1,2,4-triazole (2 mmoles), 1.042 g of caesium carbonate (3.2 mmoles) and 1.2 ml of DMF. The degree of transformation and selectivity were 100% and 98% respectively. The residue obtained following treatment was purified by silica gel chromatography (eluent: hexane/dichloromethane, 100/0 to 50/50). 264 mg of a dark yellow solid was obtained in a yield of 91%. Pale yellow needles were obtained after re-crystallisation from chloroform. The compound obtained had the following formula: The characteristics were as follows: MPt: 46 C. (CHCl3) (Lit: 46-47 C. given by Micetich, R G; Spevak, P; Hall, T W; Bains, B K; Heterocycles 1985, 23, 1645-1649); 1H NMR/CDCl3: delta8.52 (wide s, 1H, H1), 8.04 (wide s, 1H, H2), 7.53-7.65 (m, 2H, H4,8), 7.26-7.51 (m, 3H, H5,6,7); 13C NMR/CDCl3: delta 152.55 (C1), 140.88 (C2), 139.96 (C3), 129.73 (C5 and C7), 128.15 (C6), 119.99 (C4 and C8); GC/MS: Rt=14.02 min, M/Z=145, purity=100%; Rf=0.21 (eluent: dichloromethane/ethyl acetate, 90/10). Example 1.18; Preparation of 1-phenyl-1H-[1,2,4]triazole; Operating protocol A (82 C., 24 hours) was followed using 117 mg of Chxn-Py-Al (0.4 mmoles), 336 mul of iodobenzene (3 mmoles), 138 mg of 1,2,4-triazole (2 mmoles), 1.042 g of caesium carbonate (3.2 mmoles) and 1.2 ml of DMF. The degree of transformation and selectivity were 79% and 99% respectively. ; Example 1.19; Preparation of 1-phenyl-1H-[1,2,4]triazole; Example 1.18 was repeated, operating at 50 C. (72 hours). The degree of transformation and selectivity for 1-phenyl-1H-[1,2,4-triazole] were 75% and 99% respectively.

87%	With potassium phosphate; In N,N-dimethyl-formamide; at 110℃;	General procedure: 1 mmol of the compound of the formula II-1 and 2 mmol of the compound of the formula III are sequentially added to the reaction.0.5mmol% catalyst CS Cu2O,3mmol potassium phosphate and 0.5ml N,N-dimethylformamide solution, heated to 110 C to stir the reaction,After the TLC reaction was completed, the reaction was quenched with water and filtered for ethyl acetate.Washed with saturated brine, dried and concentrated.The product was obtained by silica gel column chromatography.
83%	With caesium carbonate;iron(III) acetylacetonate; copper(II) oxide; In N,N-dimethyl-formamide; at 90℃; for 30h;sealed tube;Conversion of starting material;	Preparation of 1-phenyl-1H-[1,2,4]triazole [0220] Following General Procedure A (90 0C, 30 hours), 1/-/-[1 ,2,4]triazole (104 mg, 1.5 mmol) is coupled with iodo-benzene (112 muL, 1.0 mmol). The crude brown oil is purified by flash chromatography on silica gel (eluent: dichloromethane/hexanes = 50/50) to provide 120 mg (83 % isolated yield) of the desired product as a light yellow solid. <n="50"/>007/001836_ 49 -IdentificationMp: 460C.1H NMR (400 MHz, CDCI3): delta 8.49 (s, 1 H1 H8), 8.03 (s, 1H, H7), 7.58-7.61 (m, 2H, H2i6), 7.40-7.44 (t, 2H1 H3,5), 7.31-7.33 (t, 1 H, H4).13C NMR (100 MHz, CDCI3): delta 152.62 (C7), 140.91 (C8), 136.99 (C1), 129.77 (C3,5), 128.21 (C4), 120.04 (C2i6).IR (KBr) : v (cm'1) = 3105, 2924, 2852, 1600, 1514, 1416, 1359, 1278, 1223,1152, 1055, 981 , 876, 754, 681 , 671 , 503.GC/MS: rt = 15.28 min, M/Z = 145.HRMS: 146.0721 (M+H). Theoretical: 146.0718
71%		A flask was charged with K2CO3 (12.1689 g, 88 mmol), 1H-1,2,4-triazole (2.0042 g, 29 mmol), Cu2O(430 mg, 3 mmol) and 1,10-phenanthroline (1.0452 g, 5.8 mmol) and then evacuated and back-filled with N2. Then, anhydrous DMF (20 ml) and iodobenzene (8.9764 g, 4.92 ml, 44 mmol) were added and the resulting mixture was heated to 120 C for 64 h and then diluted with CH2Cl2 (40 ml). The mixture was filtered through a pad of Celite and the residue washed with CH2Cl2 (20 ml). The resulting organic layer was washed with water (20 ml) and brine (20 ml), dried over MgSO4 and concentrated under reduced pressure. The crude mixture was purified by column chromatography (cyclohexane/ethyl acetate 8/0?2/0) to yield the product as a pale yellow solid (2.986 g, 71%).
65%		EXAMPLE 108 1-phenyltriazole 1 g (0.0145 mol) triazole 2, 0.21 g (0.00145 mol) copper(I)oxide, 0.29 g (0.00145 mol) phenantroline monohydrate and 6.01 g (0.044 mol) potassium carbonate are weighed into a Schlenk flask. After repeated evacuating and flushing with argon, 10 ml dry DMF is added. Evacuating and flushing with argon are repeated several times. Subsequently, 2.42 ml (4.43 g, 0.022 mol) of iodobenzene is added. The reaction mixture is stirred for 48 h at 100 C. under argon. After cooling 20 ml DCM is added and filtered. The solvent is removed in vacuum and the product is obtained after purification by column chromatography (KG 60, gradient petroleum ether/EtOAc 8:2 to EtOAc) as a yellowish-white solid.M 145.17 C8H7N3 Yield: 1.362 g (65%)1H-NMR DM-94 (300 MHz/DMSO): (ppm)=7.41 (t, 1H, 6-H); 7.58 (t, 2H, 5/5'-H); 7.87 (d, 2H, 4-H); 8.25 (s, 1H, 1-H); 9.31 (s, 1H, 2-H)13C-NMR DM-94 (75.475 MHz/DMSO): (ppm)=119.37 (5/5'-C); 127.78 (6-C); 129.77 (4/4'-C); 136.74 (3-C); 142.27 (2-C); 152.39 (1-C)

Reference： [1]Journal of the American Chemical Society,2007,vol. 129,p. 13879 - 13886
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19
[ 591-50-4 ]
[ 171596-36-4 ]
(6R,12AR)-6-benzo[1,3]dioxol-5-yl-2-phenyl-2,3,6,7,12,12a-hexahydropyrazino[1',2':1,6]-pyrido[3,4-b]indole-1,4-dione [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2007,vol. 17,p. 789 - 792
[2]Journal of Medicinal Chemistry,2011,vol. 54,p. 3222 - 3240

20
[ 591-50-4 ]
potassium hexacyanoferrate (II) [ No CAS ]
[ 57103-20-5 ]

Reference： [1]Synlett,2006,p. 2841 - 2845

21
[ 1126-09-6 ]
[ 591-50-4 ]
[ 94201-40-8 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium phosphate;bis(tri-t-butylphosphine)palladium(0); In 1,2-dimethoxyethane; at 100℃; for 14.0h;	A. To a solution of ethyl isonipecotate (1.00 g, 6.36 mmol) in 10 mL of anhydrous DME was added iodobenzene (1.95 g, 9.54 mmol), bis(tri-t-butylphosphine)palladium(0) (0.33 g, 0.636 mmol), and potassium phosphate (2.70 g, 12.7 mmol). The reaction mixture was heated to 100° C. and stirred for 14 hours. Solids were filtered off from the resulting mixture and the collected filtrate was concentrated under reduced pressure to provide the crude product, which was then redissolved into 10 mL of methanol. 2 mL of 1N lithium hydroxide was added to hydrolyze the ester at 80° C. for 3 hours. Solvent was evaporated off and the basic residue was acidified by 2N HCl. The aqueous mixture was extracted with EtOAc. The combined organic layers was washed with brine, dried over MgSO4, filtered, and concentrated under reduced pressure to afford the crude product which was then purified by flash column chromatography with CH2Cl2 and MeOH to yield 1-phenyl-piperidine-4-carboxylic acid as yellow solid.

Reference： [1]Patent: US2006/116368,2006,A1 .Location in patent: Page/Page column 56; 57

22
[ 591-50-4 ]
[ 2401-21-0 ]

Yield	Reaction Conditions	Operation in experiment
25.9 g (94.2%)	With chlorine; In chloroform;	EXAMPLE 6 Preparation of iodobenzene dichloride. Chlorine gas is bubbled through a solution of iodobenzene (20.4 g; 0.1 mole) in chloroform (100 ml) while the temperature of the reaction mixture is maintained at -5° C. In about 10 minutes a yellow solid precipitates and is removed by filtration. The filtrate is then further treated with chlorine gas until the formation of yellow solid ceases. The solid fractions are combined and air dried to afford 25.9 g (94.2percent) of title product.

Reference： [1]Dalton Transactions,2014,vol. 44,p. 119 - 129
[2]Patent: US4203918,1980,A

23
[ 6086-21-1 ]
[ 591-50-4 ]
[ 29945-53-7 ]

Reference： [1]Journal of the American Chemical Society,2008,vol. 130,p. 15185 - 15192
[2]Tetrahedron Letters,2008,vol. 49,p. 1045 - 1048
[3]Journal of the American Chemical Society,2007,vol. 129,p. 12404 - 12405

24
[ 591-50-4 ]
[ 4347-31-3 ]
[ 26170-85-4 ]

Reference： [1]Journal of Heterocyclic Chemistry,2008,vol. 45,p. 109 - 118

25
[ 591-50-4 ]
[ 52522-41-5 ]
[ 13406-29-6 ]
[ 180891-57-0 ]

Reference： [1]Organometallics,1996,vol. 15,p. 3708 - 3716

26
[ 591-50-4 ]
[ 63902-12-5 ]
cesium pivalate [ No CAS ]
[ 13406-29-6 ]
[ 851530-55-7 ]

Reference： [1]Journal of the American Chemical Society,2005,vol. 127,p. 4996 - 4997

27
[ 52522-40-4 ]
[ 591-50-4 ]
[ 119072-54-7 ]
[ 926042-20-8 ]

Reference： [1]Journal of Organometallic Chemistry,2007,vol. 692,p. 620 - 624

28
[ 52522-40-4 ]
[ 591-50-4 ]
[ 198766-52-8 ]
[ 603-32-7 ]
[ 352670-77-0 ]
[ 942472-59-5 ]
[ 36234-31-8 ]
rac-2,2'-bis[(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)methyl]-1,1'-biferrocene [ No CAS ]

Reference： [1]Helvetica Chimica Acta,2007,vol. 90,p. 834 - 845

29
[ 52522-40-4 ]
[ 591-50-4 ]
[ 2359-97-9 ]
[ 956274-07-0 ]

Reference： [1]Journal of Organometallic Chemistry,2007,vol. 692,p. 4486 - 4494

30
[ 591-50-4 ]
[ 6825-20-3 ]
[ 57103-20-5 ]

Yield	Reaction Conditions	Operation in experiment
85%	With copper(l) iodide; 18-crown-6 ether; potassium carbonate; In DMPU (1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone); at 170℃; for 20h;	Synthesis of Intermediate E; 3.25 g (10.0 mmol) of 3, 6-dibromocarbazole, 10.2 g (50.0 mmole) iodobenzene, 190 mg (1.0 mmole) of Cul, 132 mg (0.5 mmole) of 18-C-6, 2.76 g (20.0mmole) of K2CO3 were dissolved in 50 mL of DMPU, and stirred at 170°C for 20 hours. The mixture was cooled to room temperature and 50 mL of diethylether was added thereto. Then the mixture was washed with plenty of water and ammonium hydroxide solution. A collected organic layer was dried over MgSO4 to evaporate the solvent. The residue was purified using silica gel column chromatography to obtain 3.40 g of white solid Intermediate E (Yield: 85 percent). (NMR (CDCl3, 400MHz) delta (ppm) 7.92 (m, 2H), 7.55-7.47 (m, 6H), 7.36-7.16 (m, 3H); 13C NMR (CDCl3, 100MHz) delta (ppm) 142.6, 137.6, 130.2, 129.8, 127.4, 127.0, 122.8, 122.5, 115.3, 111.3).
75%	With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate; In toluene; at 100℃; for 24h;	To a round bottom flask Sub 2-1-6 (6.5g, 20mmol), Sub 2-1-2-1 (4.1g, 20mmol),Pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol ), NaOt-Bu (5.8g, 60mmol), were addedto toluene (210mL), respectively, and refluxed under stirring for 24 hours at 100 ° C.The organic layer was dried and the ether was extracted with water over MgSO4 andconcentrated and to the resulting organic silicagel column and recrystallized from a Sub2-1-7-1 6.0g (yield: 75percent) was obtained.
3.27 g	With palladium diacetate; tris-(o-tolyl)phosphine; sodium t-butanolate; In toluene;	2.5 g (14.9 mmol) ofcarbazole was used (utilized) to perform an NI3S bromination to synthesize 2,5-dibromocar- bazole. Then, the 2,5-dibromocarbazole and iodinated phenyl were used (utilized) to synthesize 3.72 g (9.28 mmol) of Intermediate E through a buchwald reaction.

Reference： [1]Patent: EP1921082,2008,A1 .Location in patent: Page/Page column 35-36
[2]Journal of Nanoscience and Nanotechnology,2011,vol. 11,p. 1373 - 1376
[3]Patent: KR2015/93995,2015,A .Location in patent: Paragraph 0149; 0153; 0182-0184
[4]RSC Advances,2015,vol. 5,p. 51512 - 51523
[5]Patent: KR2015/144421,2015,A .Location in patent: Paragraph 0317; 0318; 0319

31
[ 591-50-4 ]
[ 81660-73-3 ]
tert-butyl 3-phenylisonicotinate [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2009,p. 1781 - 1795

32
[ 591-50-4 ]
[ 69655-76-1 ]
POSS-F [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2008,vol. 6,p. 4662 - 4667

33
[ 90560-10-4 ]
[ 591-50-4 ]
[ 92014-01-2 ]

Yield	Reaction Conditions	Operation in experiment
		Example 16 [00381] Step 1 [00382] 1-(2,2-Diethoxy-ethylsulfanyl)-3-methoxy-benzene. To a solution of 3-methoxybenzenethiol (15.0 mL, 120 mmol) and potassium carbonate (16.6 gm, 120 mmol) in 150 mL of acetone at room temperature was added dropwise 2-bromo-1,1-diethoxy-ethane (16.5 mL, 110 mmol). The reaction mixture was stirred at room temperature for 16 hours. The solids in the reaction mixture were removed by filtration and were washed well with acetone. The filtrate was concentrated. The residue was diluted with water and extracted several times with ether. The ether layers were combined and washed with 0.5 M KOH, water, brine, and were then dried over anhydrous sodium sulfate, filtered, and concentrated to yield 28.2 gm of the title compound. [00383] Step 2 [00384] 6-Methoxy-benzo[b]thiophene. To a solution of boron trifluoride etherate (14.45 mL, 115 mmol) in 2000 mL of methylene chloride stirring in a cold water bath 20° C. was added dropwise 1-(2,2-Diethoxy-ethylsulfanyl)-3-methoxy-benzene (28.2 gm, 110 mmol) dissolved in 500 mL of methylene chloride. The addition was complete in 3 hrs. and then the reaction was warmed to room temperature for a further 1.5 hrs. The reaction mixture was then quenched with saturated sodium bicarbonate solution. The organic layer was separated and the aqueous layer was back extracted several times with methylene chloride. The organic layers were combined, dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was chromatographed on silica gel (using a gravity column) using hexanes as the eluant to yield 10.9 gm of the title compound. [00385] General Procedure for the Synthesis of Compunds of Formula IV [00386] The general scheme is outlined in Scheme 8b. Three sets of conditions are used for the acylation step and they are described below. Table 2 lists the compounds with relevant data and which procedure was used in each case. [00387] Step 3 [00388] 6-Methoxy-2-phenyl-benzo[b]thiophene. To a solution of 6-Methoxy -benzo[b]thiophene (250 mg, 1.52 mmol) in 3.7 mL THF at -20° C. was added dropwise n-butyllithium (0.67 mL, 1.67 mmol). The mixture was stirred at 0° C. for 1.5 hrs. and at room temperature for 0.5 hrs. Anhydrous zinc chloride (269 mg, 1.97 mmol) in 1.9 mL of THF was added by cannula to the reaction. The reaction was then stirred at room temperature for 15 minutes and then Pd(Ph3P)4 (70 mg, 0.06 mmol) and iodobenzene (0.22 mL, 1.97 mmol) were added and the reaction stirred at room temperature for 3 hrs. Other aromatic or heteroaromatic bromides, iodides or triflates can replace iodobenzene in this procedure. If a triflate is used 3 equivalents of anhydrous lithium chloride must be added. The reaction can be refluxed overnight to push it towards completion. The solvent was evaporated and the residue was diluted water and extracted into ethyl acetate. The combined organic layers was dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was chromatographed on silica gel using 100percent Hexanes to 1percent ethyl acetate/hexanes as the gradient eluant to yield 250 mg of the title compound. [00389] Acylation Procedure A [00390] Step 4 [00391] (6-Hydroxy-2-phenyl-benzo[b]thiophen-3-yl)-[4-(2-piperidin-1-yl-ethoxy) -phenyl]-methanone. A solution of the product from Step 3, Example 16 (272 mg, 1.13 mmol), 4-(2-Piperidin-1-yl-ethoxy)-benzoyl chloride (7.9 mL, 1.53 mmol), and titanium tetrachloride (6.62 mL, 5.66 mmol) in 16.5 mL of methylene chloride was stirred at room temperature for 6 hrs. To demethylate, ethanethiol (0.335 mL, 4.53 mmol) and AlCl3 (600 mg, 4.53 mmol) in two portions were added to the reaction and it was stirred for an additional 2.5 hrs. The reaction was quenched with saturated sodium bicarbonate solution and the solution was extracted twice with methylene chloride. The organic layers were combined, dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was chromatographed on silica gel using 1percent MeOH: CH2Cl2 to 5percent MeOH CH2Cl2 as the gradient eluant to obtain 231 mg of the title compound. [00392] 1H NMR (MeOH-d4) delta7.70(d, 2H), 7.40(m, 3H), 7.30(d, 1H), 7.25(m, 3H), 6.90(d, 1H), 6.85(d, 2H), 4.15(t, 2H), 2.75(t, 2H), 2.55(m, 4H), 1.60(m, 4H), 1.50(m, 2H)

Reference： [1]Patent: US6756388,2004,B1 .Location in patent: Page/Page column 51-52

34
[ 591-50-4 ]
[ 143360-89-8 ]
[ 3469-20-3 ]

Reference： [1]Green Chemistry,2010,vol. 12,p. 150 - 158

35
[ 591-50-4 ]
[ 886766-28-5 ]
[ 1254981-66-2 ]

Yield	Reaction Conditions	Operation in experiment
31%	With cesium hydroxide; In dimethyl sulfoxide; at 120℃; for 0.666667h;Sealed tube;	A stirred solution of <strong>[886766-28-5]4,7-diaza-spiro[2.5]octane-7-carboxylic acid tert-butyl ester</strong> (0.1 g, 0.471 mmol) [C.A.S. 886766-28-5] , iodobenzene (0.026 ml, 0.236) and CsOH (0.079 g, 0.471 mmol) in DMSO (1 ml) was heated in a sealed tube at 1200C for 20 min. After cooling, additional <strong>[886766-28-5]4,7-diaza-spiro[2.5]octane-7-carboxylic acid tert-butyl ester</strong> (2 eq.) was added, and the mixture was then heated at 1200C for 20 min. The mixture was cooled.The mixture was washed with NH4Cl (aqueous sat. solution) was added and extracted with Et2O. The organic phase was separated, washed with water, dried (Na2SO4) and concentrated in vacuo. The crude product was purified by manifold (Sep-Pak.(R). silica cartridge; DCM as eluent). The desired fractions were collected and concentrated in vacuo to yield intermediate D61 (0.021 g, 31percent) as a white solid.

Reference： [1]Patent: WO2010/130424,2010,A1 .Location in patent: Page/Page column 121-122

36
[ 591-50-4 ]
[ 1569-16-0 ]
[ 1256347-50-8 ]

Reference： [1]Organic Letters,2010,vol. 12,p. 5359 - 5361

37
[ 591-50-4 ]
[ 57103-20-5 ]

Reference： [1]Patent: EP2343277,2011,A2
[2]Journal of Materials Chemistry,2011,vol. 21,p. 4918 - 4926
[3]Journal of Materials Chemistry,2011,vol. 21,p. 9139 - 9148
[4]Journal of the Chinese Chemical Society,2012,vol. 59,p. 331 - 337
[5]Journal of Materials Chemistry,2012,vol. 22,p. 4527 - 4534
[6]Journal of the Chinese Chemical Society,2013,vol. 60,p. 579 - 589
[7]Patent: CN104650044,2017,B

38
[ 591-50-4 ]
[ 70357-66-3 ]
[ 70357-61-8 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2011,vol. 21,p. 5487 - 5492

39
[ 591-50-4 ]
[ 6358-06-1 ]
4-chloro-3-phenoxybenzenamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With 2-Picolinic acid; potassium phosphate; copper(l) iodide; In dimethyl sulfoxide; at 80℃; for 24h;Inert atmosphere;	[00599] To a mixture of copper(I) iodide (0.96 g, 5 mmol), 2-picolinic acid (1.23 g, 10 mmol), iodobenzene (10.2 g, 50 mmol), <strong>[6358-06-1]5-amino-2-chlorophenol</strong> (10.2 g, 70 mmol) and K3PO4 (21.2g, 100 mmol), DMSO (150 mL) was added under nitrogen. The reaction mixture was stirred vigorously for 24 h at 80 C. The reaction mixture was cooled to room temperature. Ethyl acetate (500 mL) and H20 (300 mL) were added. The organic layer was separated and the aqueous layer was extracted twice more with ethyl acetate (200 mL). Combined organic layers were dried over anhydrous Na2S04 and concentrated in vacuo. The crude product was purified by column chromatography (Si02, petrol ether/EtOAc 70:30) to give the title compound 4-chloro-3-phenoxybenzenamine (7.5 g, 34 mmol, 68%) as a white solid. ESI-MS (EI+, m/z): 220.2[M+H]+.

Reference： [1]Patent: WO2018/191146,2018,A1 .Location in patent: Paragraph 00599
[2]Journal of the American Chemical Society,2011,vol. 133,p. 15686 - 15696

40
[ 591-50-4 ]
[ 618442-57-2 ]

Reference： [1]Journal of Materials Chemistry,2011,vol. 21,p. 9139 - 9148

41
[ 2401-21-0 ]
[ 82833-74-7 ]
[ 591-50-4 ]
[ 4323-64-2 ]

Reference： [1]Heteroatom Chemistry,2012,vol. 23,p. 352 - 372

42
[ 2401-21-0 ]
[ 82833-73-6 ]
[ 4124-92-9 ]
[ 591-50-4 ]

Reference： [1]Heteroatom Chemistry,2012,vol. 23,p. 352 - 372

43
[ 591-50-4 ]
[ 19430-93-4 ]
[ 95452-53-2 ]
[ 80967-16-4 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium phosphate; C30H25ClN2P2Pd; In N,N-dimethyl-formamide; at 110℃; for 24h;Sealed tube;	General procedure: A sealed tube was charged with aryl halide (1.0 mmol), fluoroalkyl-substituted ethylenes (1.1 mmol), K3PO4 (1.0 mmol), DMF (2 mL) and catalyst (1 molpercent Pd), the mixture was stirred at a certain temperature for a certain time. After being cooled to room temperature, the mixture was filtered. The solvent and excess fluoroalkyl-substituted ethylenes were removed under reduced pressure and the residue was purified by F-SPE technique. Menthol and H2O (v/v = 8:2) were used as fluorophobic elution, while H2O were used as fluorophilic elution. The product was obtained from fluorous phase in high purity.

Reference： [1]Journal of Fluorine Chemistry,2013,vol. 146,p. 6 - 10

44
[ 14432-12-3 ]
[ 591-50-4 ]
[ 73183-34-3 ]
[ 42260-39-9 ]

Reference： [1]Journal of Organic Chemistry,2013,vol. 78,p. 1923 - 1933

45
[ 591-50-4 ]
[ 63139-21-9 ]
[ 5707-44-8 ]

Yield	Reaction Conditions	Operation in experiment
96%	With potassium carbonate; In ethanol; water; at 60℃; for 1h;Green chemistry;	General procedure: A mixture of aryl halide (0.125mmol), phenylboronic acid(0.126mmol), K2CO3(0.187mmol), in 0.5ml H2O:EtOH(1:1) and Pd(II)NA2SMNP (0.0006g, 0.02mol%) wasstirred at 60C for the appropriate of time. The progressof the reaction was monitored by TLC. After completionthe reaction, the catalyst was removed with an externalmagnet and washed with EtOH, dried and used directly fora subsequent round of reaction without further purification.Then, desired product (liquid phase) was extracted byplate chromatography eluted with n-hexane/EtOAc (10:1).
94%	With C22H28Cl2O4PdS2; caesium carbonate; In ethanol; at 78℃; for 4h;	General procedure: A one-pot mixture of aryl halide (0.75 mmol), arylboronic acid(1 mmol), catalyst (0.005 mol%), Cs2CO3 (1.5 mmol) and EtOH(2 ml) was heated to 78 C for 4 h. The reactions progress was monitoredby thin layer chromatography (TLC). After completion of thereaction, the mixture was cooled to room temperature and dilutedwith n-hexane (15 ml) and water (15 ml). The resulting organiclayer was twice washed with brine (15 ml) and dried over CaCl2,filtered and purified by recrystallization or silica gel column chromatography(n-hexane: EtOAc, 80:20) and analyzed by NMR spectroscopy (1H and 13C).
91%	With C68H58Cl4Cu2O2P4; caesium carbonate; In N,N-dimethyl-formamide; at 130℃; for 24h;Schlenk technique; Inert atmosphere;Catalytic behavior;	General procedure: In a typical run, a 25 ml Schlenk tube was charged with amixture of an aryl halide (0.5 mmol), 4-ethyl phenylboronic acid(0.75 mmol), catalyst (5 mol%), Cs2CO3 (1.5 mmol) and DMF (2 ml)under nitrogen. The tube was placed in a 130 C oil bath and stirredfor 24 h. The reaction progress was monitored by thin-layer chromatography(TLC). The reaction mixture was then cooled to roomtemperature and then 15 ml water was added, followed byextraction with n-hexane (15 ml) The combined organic layer werewashed with brine (3 15 ml) and dried over CaCl2. The solventwas evaporated and a crude product was obtained. The purifiedproducts were identified by comparison of their 1H and 13C NMRspectral data with the literature [33]. Yields were calculated againstconsumption of the aryl halides.

91%	With [Ph2PCH2PPh2CH=C(O)(C10H7)]PdCl2}; caesium carbonate; In water; at 80℃; for 0.333333h;	General procedure: A reaction tube was charged with the required aryl halide (0.75 mmol), aryl boronic acid (1 mmol), Pd catalyst(0.001 mmol) and Cs2CO3 (1.5 mmol) in water (2 mL). The reaction mixture was stirred for the required period of time at 80 C until completion of the reaction, as monitored by TLC. The final reaction mixture was cooled to room temperature and extracted with n-hexane. The combined organic phase was dried with CaCl2, solvent was removed, and the product was recrystallized from ethanol. Yields were calculated against consumption of the arylhalides, and pure products were identified by FTIR, 1H and 13C NMR spectroscopy and melting point analysis (See supplementary data).
91%	With sodium t-butanolate; In water; at 28℃; for 4h;Irradiation;Catalytic behavior;	General procedure: Aryl iodide (1 mmol), aryl boronic acid (1.2 mmol), nano Pd/TiO2 (15 mg), H2O-PEG (5 mL, volume ratio of 1:1), NaOC(CH3)3 (3 mmol) were placed in a 10 mL Pyrex round bottom flask. The flask was covered with a rubber stopper. The reaction vessel was stirred at ambient temperature (28 C) under visible light obtained by irradiation of 15 W flexible white LED strips placed on the walls inside the box spirally and the reaction flask was placed in the center of the box (see SM, S1). The temperature of the reaction system was kept at ambient temperature with an air conditioner and a mechanical fan mounted on the box. After completion of the reaction (monitoring by GC), the catalyst was removed by centrifuging and the resulting mixture was extracted with AcOEt (2×10 mL). The organic layers were combined and dried over anhydrous sodium sulfate (Na2SO4) and further concentrated under reduced pressure. The desired product was purified by column chromatography (CC) on silica gel using n-hexane/ethyl acetate (40:1, 20:1).
83%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 100℃; for 6h;Inert atmosphere;	A mixture of iodobenzene (4.08 g, 20 mmol), 4-ethylphenylboronic acid (2.25 g, 15 mmol), Pd(PPh3)4 (0.52 g, 0.45 mmol) and K2CO3 (4.2 g, 30 mmol) in 1,4-dioxane (20 mL) and water (20 mL) was stirred at 100 C for 6 h under N2. The mixture was extracted with EtOAc (3 x 10 mL), and the combined organic extracts were then washed with brine and dried over MgSO4. After the solvent was removed in vacuo, the crude product was purified by column chromatography on silica gel with PE as eluent to yield the corresponding product. 4-Ethyl-1,1'-biphenyl (3j)[10], colorless oil, 83% yield, 1H NMR (400 MHz, CDCl3) delta 7.58(d, 2H, J = 8.4 Hz), 7.52 (d, 2H, J = 8.0 Hz), 7.43 (t, 2H, J = 7.2 Hz), 7.30 (m, 3H), 2.70(q, 2H, J = 7.6 Hz), 1.28 (t, 3H, J = 7.6 Hz). 13C NMR (100 MHz, CDCl3) delta 143.6, 141.4,138.9, 129.0, 128.6, 127.3, 127.3, 127.2, 28.8, 15.9. IR (neat) 2965, 1487, 836, 759, 696 cm-1.
81%	With triethylamine; In neat (no solvent); at 70℃; for 2h;Sealed tube; Irradiation;	General procedure: In a typical reaction, a mixture of aryl halid (0.2mmol),arylboronic acid (0.22 mmol), Et3N(0.4 mmol) and TiO2-AA-Pd nano hybrid (0.15mol%) was added in a10 mL Pyrex test tube and sealed with septum cap. Then thereaction mixture transferred into a reactor chamber and irradiate dunder magnetic stirring using a CFL lamp (philips,wavelength in the range 390-750nm, 40W, 1.1Wm-2) asthe visible light source at 70C for appropriate time. Aftercompletion of the reaction, TiO2-AA-Pd nanohybrid wasextracted by adding of ethanol (5mL) followed by centrifugingand decantation (3 × 5mL ethanol). Then, desired product(liquid phase) was extracted by plate chromatographyeluted with n-hexane/EtOAc (10/2).
61%	With potassium carbonate; In water; N,N-dimethyl-formamide; at 80℃; for 4h;	General procedure: The aryl halide (0.5 mmol), arylboronic acid (0.75 mmol), Cell-NHC-Pd (0.75 mol%), K2CO3(1 mmol) and DMF:H2O (1:1) (2.5 mL)were successively added into a 25 mL round bottom flask. The mixture was stirred vigorously at 80 C for the varying specific length of time based on each different substrate. After reaction completion, the solid catalyst was filtered off. The filtrate was extracted with ethyl acetate (3 × 5 mL), washed with water and brine three times, and then dried over anhydrous MgSO4. The MgSO4 was then filtered off. After removal of the solvent, the crude product was purified by preparative TLC (eluent: petroleum ether/ethyl acetate, 20/1) to give the desired product and calculate the yield.
93%Spectr.	With potassium carbonate; In water; N,N-dimethyl-formamide; at 100℃; for 4h;	General procedure: The efficiency of the designed nanocatalyst was verified in Suzuki cross-coupling reactions. General procedure for catalytic test using the nanocatalyst is as follows. Solvent dimethylformamide (DMF)/H2O (3:1), aryl halide (0.5 mmol),aryl boronic acid (0.6 mmol), K2CO3 (2 mmol), nanocatalyst(1 mol %), and a small stirring bar were added to a round bottom flask (25 mL). The flask containing reaction mixture was placed in an oil bath (100 C) and stirred under air atmosphere. After completion of reaction, the mixture was cooled to room temperature and the nanocatalyst was separated using a magnet. The separated nanocatalyst was washed several times with DMF. Finally the products wer eanalyzed by a gas chromatography mass spectrometer (GCMS).
93%Chromat.	With potassium carbonate; In water; N,N-dimethyl-formamide; at 100℃; for 1.5h;	General procedure: Nanocomposite Pd catalyst (1 mol%) was added to a round-bottom flask (25 ml) and dispersed in dimethylformamide(DMF)/H2O (2:1) mixture. Then, aryl halide (0.5 mmol), aryl boronic acid (0.6 mmol), K2CO3(1.5 mmol), and a small stirring bar wereadded to the round-bottom flask. The flask containing reaction mixture was placed in an oil bath (100C) and stirred under airatmosphere. After completion of reaction, the mixture was cooled to room temperature and the nanocomposite Pd catalyst was separated using a magnet. The separated catalysts were washed severaltimes with DMF. Finally the products were analyzed by a GC-MS.

Reference： [1]Helvetica Chimica Acta,2015,vol. 98,p. 805 - 818
[2]Catalysis Letters,2018,vol. 148,p. 3165 - 3177
[3]Applied Organometallic Chemistry,2018,vol. 32
[4]Polyhedron,2016,vol. 117,p. 273 - 282
[5]Tetrahedron,2017,vol. 73,p. 5624 - 5633
[6]Inorganic Chemistry Communications,2014,vol. 47,p. 123 - 127
[7]Applied Organometallic Chemistry,2019,vol. 33
[8]Journal of Organometallic Chemistry,2014,vol. 761,p. 111 - 119
[9]Transition Metal Chemistry,2015,vol. 40,p. 657 - 663
[10]Catalysis Communications,2018,vol. 111,p. 10 - 15
[11]Synthesis,2017,vol. 49,p. 4007 - 4016
[12]Catalysis Letters,2019
[13]Carbohydrate Polymers,2014,vol. 114,p. 476 - 483
[14]Chemical Communications,2013,vol. 49,p. 4779 - 4781
[15]Journal of Coordination Chemistry,2013,vol. 66,p. 411 - 423
[16]Bulletin of the Korean Chemical Society,2013,vol. 34,p. 1477 - 1480
[17]Applied Catalysis A: General,2014,vol. 476,p. 133 - 139

46
[ 591-50-4 ]
[ 172732-52-4 ]
[ 24973-49-7 ]

Reference： [1]Organic Letters,2013,vol. 15,p. 2742 - 2745

47
[ 591-50-4 ]
[ 1092351-82-0 ]
methyl 1-methyl-3-phenyl-1H-indazole-5-carboxylate [ No CAS ]

Reference： [1]Chemical Science,2013,vol. 4,p. 2374 - 2379

48
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Reference： [1]Organic Process Research and Development,2002,vol. 6,p. 525 - 532

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