* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference:
[1] Journal of the American Chemical Society, 2013, vol. 135, # 45, p. 16841 - 16844
2
[ 90-14-2 ]
[ 122-04-3 ]
[ 636-98-6 ]
[ 879-18-5 ]
Reference:
[1] Journal of the American Chemical Society, 2018, vol. 140, # 32, p. 10140 - 10144
3
[ 90-14-2 ]
[ 100-20-9 ]
[ 1711-02-0 ]
[ 879-18-5 ]
Reference:
[1] Journal of the American Chemical Society, 2018, vol. 140, # 32, p. 10140 - 10144
4
[ 90-14-2 ]
[ 86-74-8 ]
[ 22034-43-1 ]
Reference:
[1] New Journal of Chemistry, 2017, vol. 41, # 2, p. 559 - 568
[2] Organic Letters, 2015, vol. 17, # 14, p. 3640 - 3642
5
[ 13922-41-3 ]
[ 90-14-2 ]
Yield
Reaction Conditions
Operation in experiment
89%
With 1,10-Phenanthroline; oxygen; potassium iodide; copper(ll) bromide In N,N-dimethyl-formamide at 80℃; for 20 h;
General procedure: under oxygen, a sealed reaction tube was charged with KX (X = I, Br) (0.2 mmol), arylboronic acid (0.3 mmol), CuBr2 (4.5 mg, 10 mol percent), 1,10-phen (7.2 mg, 20 mol percent) and DMF (2 mL). The mixture was stirred at 80 or 130 °C. After the completion of the reaction, the solvent was evaporated under reduced pressure and the residue was purified by flash column chromatography on silica gel to give the product.
87%
With iodine; potassium carbonate In acetonitrile at 80℃; for 9 h; Inert atmosphere; Schlenk technique; Sealed tube
General procedure: Arylboronic acid 1 (0.5 mmol) and K2CO3 (1 mmol, 138.0mg) were added to a 20 mL Schlenk-tube equipped with amagnetic stir bar. The tube was evacuated twice and backfilledwith N2. MeCN (2 mL) and I2 (0.75 mmol, 191 mg)were added to the tube at r.t. under a stream of N2, and thetube was sealed and placed into a pre-heated oil bath at 80 °Cfor 8–12 h. The resulting solution was cooled to r.t. and H2O(10 mL) was added. The aq layer was extracted with EtOAc (3 × 5 mL). For products 2s and 2t, HCl (1 M) was added tothe aq solution until pH 2 before extraction. The combinedorganic phase was dried over anhydrous Na2SO4, filteredand concentrated by rotary evaporation. Purification of theresidue by column chromatography on silica gel providedthe desired product 2a–v
86%
With perfluoroisopropyl iodide; copper; hydroquinone In N,N-dimethyl-formamide at 20℃; for 24 h;
General procedure: (4-Nitrophenyl)boronic acid (0.067 g, 0.4 mmol), copper powder (0.0052 g, 0.08 mmol,), (CF3)2CFI (0.178 g, 0.6 mmol), and DMF (2 mL) were placed in a closed tube with a rubber stopper. The mixture was reacted at room temperature equipped with an air balloon for 24 h. The resulting suspension was poured into water and extracted with ethyl acetate. The organic layer was dried over anhydrous Na2SO4 and concentrated to dryness. The crude product was purified by flash column chromatography on silica gel using petroleum ether/ethyl acetate = 20: 1 (v/v) as eluent to give 0.086 g of 2j as a light yellow solid (0.35 mmol, 87percent).
85%
With copper(II) nitrate trihydrate; iodine In acetonitrile at 20℃; for 6 h; Sealed tube
General procedure: 0.05 mmol Cu(NO3)2·3H2O, 1 mmol I2, 1 mmol arylboronic acids and 0.8 mL acetonitrile were added into an about 15 mL tube. Subsequently, the reaction tube was sealed to perform the reaction for 6 h without inert gas protection. Once the reaction time was reached, 10 mL water was added. The mixture was then extracted with dichloromethane (3 x 15 mL). The combined organic layers were washed with aqueous sodium hyposulfite, distilled water, dried over Na2SO4, filtered and concentrated. The crude product was purified by column chromatography and identified by 1H NMR, 13C NMR or GC-MS data.
Reference:
[1] Tetrahedron Letters, 2011, vol. 52, # 16, p. 1993 - 1995
[2] Synlett, 2014, vol. 25, # 7, p. 995 - 1000
[3] Journal of Fluorine Chemistry, 2016, vol. 189, p. 59 - 67
[4] Chemistry - A European Journal, 2011, vol. 17, # 20, p. 5652 - 5660
[5] Catalysis Communications, 2013, vol. 32, p. 15 - 17
6
[ 90-11-9 ]
[ 90-14-2 ]
Yield
Reaction Conditions
Operation in experiment
85%
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; Inert atmosphere Stage #2: With iodine In tetrahydrofuran; hexane at -78 - 20℃; for 0.25 h; Inert atmosphere
General procedure: Aryl bromide (10 mmol) was dissolved in dry THF (30 mL) and cooled to -78 °C under anargon atmosphere. n-Butyllithium (1.6 M in n-hexane; 7.5 mL; 12 mmol) was addeddropwise. After 15 minutes a solution of I2 (3.81 g; 15 mmol) in dry THF (10 mL) was addedand the reaction mixture was allowed to warm to room temperature overnight.For workup the reaction mixture was concentrated in vacuo. H2O was added to the residueand it was extracted with DCM (3x). The combined organic phases were washed withsaturated Na2S2O5 solution and H2O. After drying over MgSO4 and concentration underreduced pressure, the crude product was purified by column chromatography.
92 %Chromat.
With copper(I) oxide; <i>L</i>-proline; potassium iodide In ethanol at 110℃; for 30 h; Schlenk technique; Inert atmosphere; Sealed tube
General procedure: A Schlenk tube was charged with Cu2O (7.2 mg, 10 molpercent), l-proline (11.5 mg, 20 molpercent), aryl (or heteroaryl) bromide (1 or 3,0.50 mmol), potassium iodide (KI) (249 mg, 0.75 mmol), and EtOH(1.5 mL) under nitrogen atmosphere. The Schlenk tube was sealedwith a teflon valve, and then the reaction mixture was stirred at110C for a period (the reaction progress was monitored by GCanalysis). After the reaction was completed, GC yield of high volatileproduct was determined using an appropriate internal standard(chlorobenzene or 1-chloro-4-methylbenzene) or the solvent wasremoved under reduced pressure. The residue obtained was puri-fied via silica gel chromatography (eluent: petroleum ether/ethylacetate = 10/1) to afford aryl iodides 2a–2o or heteroaryl iodides4a–4g.
Reference:
[1] Beilstein Journal of Organic Chemistry, 2011, vol. 7, p. 1499 - 1503
[2] Synlett, 2013, vol. 24, # 20, p. 2730 - 2734
[3] Synthetic Communications, 2012, vol. 42, # 2, p. 170 - 175
[4] Journal of the American Chemical Society, 2015, vol. 137, # 26, p. 8328 - 8331
[5] Catalysis Today, 2016, vol. 274, p. 129 - 132
[6] Catalysis Science and Technology, 2017, vol. 7, # 10, p. 2110 - 2117
7
[ 166328-07-0 ]
[ 90-14-2 ]
Yield
Reaction Conditions
Operation in experiment
66%
With caesium tribromide In water; N,N-dimethyl-formamide at 80℃; for 3 h;
General procedure: To a solution of trifluoroborate (1 mmol) in 3 mL of aqueous DMF (2:1 v/v), cesium triiodide (1 mmol) was added. The mixture was stirred at 80 °C for the appropriate time (Table 3) and then diluted with 10 mL of ether. The aqueous layer was extracted twice with ether (5 mL) and the combined organic phase was dried over anhydrous Na2SO4. After evaporation of the solvent the residue was purified by silica gel column chromatography [elute: hexane (or pentane)-ethyl acetate (or Et2O)].
Reference:
[1] Journal of the American Chemical Society, 2017, vol. 139, # 33, p. 11527 - 11536
17
[ 85-46-1 ]
[ 90-14-2 ]
Reference:
[1] Bulletin of the Chemical Society of Japan, 1993, vol. 66, # 7, p. 2121 - 2123
[2] Bulletin of the Chemical Society of Japan, 1993, vol. 66, # 7, p. 2121 - 2123
18
[ 1730-04-7 ]
[ 90-14-2 ]
[ 569-41-5 ]
[ 90-12-0 ]
[ 199111-38-1 ]
Reference:
[1] Journal of Organic Chemistry, 1997, vol. 62, # 25, p. 8681 - 8686
19
[ 91-20-3 ]
[ 612-55-5 ]
[ 90-14-2 ]
Reference:
[1] Russian Journal of Organic Chemistry, 2005, vol. 41, # 6, p. 855 - 859
[2] Journal of Organic Chemistry, 2018, vol. 83, # 2, p. 930 - 938
20
[ 16176-22-0 ]
[ 90-14-2 ]
Reference:
[1] Journal of the American Chemical Society, 2016, vol. 138, # 37, p. 12073 - 12076
21
[ 98978-44-0 ]
[ 90-14-2 ]
Reference:
[1] Journal of the American Chemical Society, 2016, vol. 138, # 37, p. 12073 - 12076
22
[ 110055-84-0 ]
[ 64-19-7 ]
[ 90-14-2 ]
[ 7782-50-5 ]
Reference:
[1] Journal of the American Chemical Society, 1959, vol. 81, p. 2374,2376
[2] Journal of the American Chemical Society, 1959, vol. 81, p. 2374,2376
[3] Journal of the American Chemical Society, 1959, vol. 81, p. 2374,2376
[4] Journal of the American Chemical Society, 1959, vol. 81, p. 2374,2376
23
[ 1576-35-8 ]
[ 149512-01-6 ]
[ 119-64-2 ]
[ 90-14-2 ]
[ 103-19-5 ]
[ 52258-16-9 ]
Reference:
[1] Advanced Synthesis and Catalysis, 2016, vol. 358, # 21, p. 3368 - 3372
24
[ 607-51-2 ]
[ 90-14-2 ]
Reference:
[1] Justus Liebigs Annalen der Chemie, 1868, vol. 147, p. 173
25
[ 91-20-3 ]
[ 612-55-5 ]
[ 90-14-2 ]
[ 36316-88-8 ]
Reference:
[1] Journal of Catalysis, 1994, vol. 147, # 1, p. 186 - 198
[2] Journal of Catalysis, 1994, vol. 147, # 1, p. 186 - 198
26
[ 91-20-3 ]
[ 108-67-8 ]
[ 2100-25-6 ]
[ 604-53-5 ]
[ 22187-05-9 ]
[ 90-14-2 ]
Reference:
[1] Journal of the American Chemical Society, 1980, vol. 102, # 21, p. 6504 - 6512
27
[ 624-74-8 ]
[ 703-55-9 ]
[ 90-14-2 ]
Reference:
[1] Chemische Berichte, 1954, vol. 87, p. 1148,1153
28
[ 1730-04-7 ]
[ 4518-98-3 ]
[ 90-14-2 ]
[ 162132-31-2 ]
Reference:
[1] Journal of Organometallic Chemistry, 1994, vol. 484, # 1-2, p. 137 - 146
29
[ 91-20-3 ]
[ 90-14-2 ]
[ 90-13-1 ]
Reference:
[1] Journal of the Chemical Society. Perkin Transactions 2, 2001, # 9, p. 1516 - 1521
30
[ 7790-99-0 ]
[ 66172-96-1 ]
[ 90-14-2 ]
[ 5153-28-6 ]
Reference:
[1] Journal of the Chemical Society, 1921, vol. 119, p. 913 - 926
[2] , Gmelin Handbook: Bi: Org.Verb., 1.3.3.2.5, page 80 - 82,
31
[ 1950-78-3 ]
[ 91-20-3 ]
[ 90-14-2 ]
[ 2943-42-2 ]
[ 104-15-4 ]
[ 108-88-3 ]
[ 71-43-2 ]
Reference:
[1] Phosphorus and Sulfur and the Related Elements, 1984, vol. 21, p. 321 - 326
32
[ 30365-83-4 ]
[ 90-14-2 ]
[ 88-89-1 ]
Reference:
[1] Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical & Analytical, 1986, vol. 25, # 5, p. 413 - 415
33
[ 506-78-5 ]
[ 67-66-3 ]
[ 33397-22-7 ]
[ 90-14-2 ]
Reference:
[1] Journal of the Chemical Society, 1921, vol. 119, p. 916
34
[ 60-29-7 ]
[ 67-66-3 ]
[ 7790-99-0 ]
[ 66172-96-1 ]
[ 90-14-2 ]
[ 5153-28-6 ]
Reference:
[1] Journal of the Chemical Society, 1921, vol. 119, p. 916
EXAMPLE 8 5-Methyl-1-(1-naphthyl)-2-(1H)-pyridone 5-Methyl-1-(1-naphthyl)-2-(1H)-pyridone is prepared by the reaction of 5-methyl-2-(1H)-pyridone and alpha-iodonaphthalene following the procedure of Example 1 but substituting anhydrous sodium carbonate for the potassium carbonate; yield 68%.
5,11-di-1-naphthyl-5,11-dihydroindolo[3,2-b]carbazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With potassium carbonate; In water; toluene;
EXAMPLE III Synthesis of 5,11-di-1-naphthyl-<strong>[6336-32-9]5,11-dihydro<strong>[6336-32-9]indolo[3,2-b]carbazole</strong></strong> (3): A 200 milliliter 3-necked round bottom flask equipped with a mechanical stirrer, reflux condenser, and argon inlet was purged with argon and then charged with <strong>[6336-32-9]5,11-dihydro<strong>[6336-32-9]indolo[3,2-b]carbazole</strong></strong> (5.1 grams, 0.02 mol), 1-iodonaphthalene (10.16 grams, 0.04 mol), copper sulfate pentahydrate (0.25 gram, 1.0 mmol), potassium carbonate (5.52 grams, 0.04 mol), and n-tridecane (5.0 milliliters). Under an argon atmosphere, the reaction mixture was heated to about 250°C with a heating mantle and allowed to proceed at this temperature to completion in about 6 hours. The reaction mixture was cooled to about 100°C, and 100 milliliters of toluene and 15 milliliters of water were then added with vigorous stirring for 30 minutes. The resulting two phase mixture was transferred into a separatory funnel and the layers separated. The organic phase which contains the desired product was washed with water, treated with 25 grams of alumina under an argon atmosphere, and filtered.
With copper(l) iodide; 1,10-Phenanthroline; potassium carbonate; In N,N-dimethyl-formamide; at 120℃; for 10h;
General procedure: To a solution of CuI (0.025 mmol, 4.8 mg), 1,10-phenanthroline (0.05 mmol, 9 mg) and K2CO3 (0.65 mmol, 90 mg) in reagent-grade DMF (1.5 mL) was added aryl iodides (0.6 mmol) followed by thiols (0.5 mmol) in DMF (1.5 mL). The reaction mixture was then stirred at 120 oC for 10 h. The mixture was allowed to cool to room temperature. Ethyl acetate (10 mL) and H2O (10 mL) were added, and the organic phase was separated. The aqueous phase was extracted with ethyl acetate (10 mL×3). The combined organic phases were washed with saturated brine, dried over anhydrous Na2SO4. The organic solvent was removed in vacuo, and the residue was purified by chromatography on silica gel to afford the desired products.
With bis(benzonitrile)palladium(II) dichloride; cesium fluoride; (R)-4-phenyldinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepine; In tetrahydrofuran; at 70℃; for 4h;Inert atmosphere; Schlenk technique;
General procedure: A Schlenk tube was charged with 0.25 mmol of naphthyl halide, 0.0025 mmol of Pd precursor, 0.00375 mmol of the appropriate chiral ligand, 0.5 mmol of boronic acid, and 1.25 mmol of base. Anhydrous solvent was added, the flask was sealed and the mixture was stirred and heated at the corresponding temperature. The reaction mixture was treated with 10 mL of distilled water, extracted with 3 x10 mL of CH2Cl2, dried over MgSO4, and purified by flash chromatography to obtain the corresponding products. The conversion and selectivity was monitored by gas chromatography. The ee values were determined by High Performance Liquid Chromatography.
With copper(l) iodide; ethylenediamine; sodium t-butanolate; In toluene; at 100℃; for 4.0h;
General procedure: CuI (10mol%) and EDA (10mol%) were added to a mixtureof O-alkyl carbamate (1mmol), NaOtBu (1.5mmol) and aryl halide (1mmol) in 2mL toluene and the mixture wasstirred for the appropriate time, which was determined byTLC monitoring, at 100C. After completion of the reaction,the catalyst was removed by filtration and 20mL H2Owas added to the filtrate. The resultant mixture was extractedwith CHCl3.Then the organic phase was washed with water(2 × 10mL) and dried over anhydrous Na2SO4.After evaporationof CHCl3under reduced pressure, the correspondingcrude product was purified by flash chromatography to givethe desired pure cross-coupling product in good to excellentyield. In the case of using arylboronic acids as couplingpartners, Cu(OAc)2 was employed instead of CuI.
(4-methoxy-2-nitrophenyl)(naphthalen-1-yl)selane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
75%
With 1,10-Phenanthroline; oxygen; copper diacetate; potassium carbonate; In toluene; at 100℃; for 24h;
At room temperature, <strong>[33844-21-2]2-nitro-4-methoxybenzoic acid</strong> (0.4 mmol, 1 equiv), elemental selenium (1.2mmol, 3equiv), 1- iodonaphthalene (1.2mmol, 3equiv), Cu (OAc) 2 ( 0.04mmol), 1,10- phenanthroline (0.04 mmol), potassium carbonate (1.2mmol, 3equiv) and 2mL of toluene was added to the reaction tube, then filled with oxygen, and substituted three times, the reaction under an oxygen environment 100 the reaction was stirred 24h deg.] C temperature. By the end of the reaction was monitored by thin layer chromatography, the reaction mixture was cooled, filtered and then ethyl acetate was added, and then spin off the solvent, the product obtained was isolated by column chromatography (eluent: petroleum ether: diethyl ether = 98), the product is yellow liquid, yield 75%, by weight of the product is 144mg.
6-methoxy-2-(naphthalen-1-yl)quinazolin-4(3H)-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
90%
With 1,8-diazabicyclo[5.4.0]undec-7-ene; In N,N-dimethyl-formamide; at 120℃; under 7500.75 Torr; for 20h;Inert atmosphere; Autoclave;
General procedure: A 12mL vial was charged with MCM-41-2P-Pd(OAc)2 (2molpercent), 2-aminobenzamide (1mmol), aryl iodide (1mmol) (if solid) and a stirring bar. Then, DMF (2mL), aryl iodide (1mmol) (if liquid) and DBU (2mmol) were injected by syringe under an argon atmosphere. The vial was placed in an alloy plate, which was transferred into a 300mL Parr Instruments 4560 series autoclave under an argon atmosphere. After flushing the autoclave three times with CO, a pressure of 10bar CO was fixed at ambient temperature. The autoclave was heated for 20hat 120°C. After completion of the reaction, the autoclave was cooled to room temperature and the pressure was released carefully. The reaction mixture was diluted with ethyl acetate (10mL) and filtered. The palladium catalyst was washed with distilled water (2×5mL) and acetone (2×5mL), and reused in the next run. The filtrate was concentrated in vacuo and the pure product was isolated by either washed with water, ethyl acetate and finally hexane or recrystallization from MeOH.
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate; sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; at 130 - 135℃; for 48h;
First, 15.2 g (60 mmol) of 1-iodonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.), 6.31 g (30 mmol) of 4,4?-methylene bis(cyclohexylamine) (manufactured by Tokyo Chemical Industry Co., Ltd.), 8.07 g (84 mmol) of sodium t-butoxide, 0.09 g (0.2 mmol) of 2-dicyclohexylphosphino-2?,6?,-dimethoxybiphenyl (manufactured by Aldrich), and 0.021 g (0.1 mmol) of palladium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) were dispersed in 30 mL of xylene and reacted at 130 C. to 135 C. for 48 hours. After the reaction was completed, the reaction product was cooled to room temperature and mixed with water for extraction. Next, the product thus obtained was dried and concentrated with magnesium sulfate, thereby obtaining the following intermediate A-1 in an amount of 8.5 g (yield 70%). The compound thus obtained was confirmed to be a target compound from the following analysis results: MS (ESI) (m/z): 407 (M+H), Elemental analysis values: CHN measurement values (85.47%, 8.02%, 6.72%); theoretical values (85.26%, 8.11%, 6.63%)
70%
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate; sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; at 130 - 135℃; for 48h;
First, 15.2 g (60 mmol) of 1-iodonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.), 6.31 g (30 mmol) of 4,4?-methylene bis(cyclohexylamine) (manufactured by Tokyo Chemical Industry Co., Ltd.), 8.07 g (84 mmol) of sodium t-butoxide, 0.09 g (0.2 mmol) of 2-dicyclohexylphosphino-2?,6?,-dimethoxybiphenyl (manufactured by Aldrich), and 0.021 g (0.1 mmol) of palladium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) were dispersed in 30 mL of xylene and reacted at 130 C. to 135 C. for 48 hours. After the reaction was completed, the reaction product was cooled to room temperature and mixed with water for extraction. Next, the product thus obtained was dried with magnesium sulfate and concentrated, thereby obtaining the following intermediate A-1 in an amount of 8.5 g (yield 70%). The compound thus obtained was confirmed to be a target compound from the following analysis results: MS (ESI) (m/z): 407 (M+H), Elemental analysis values: CHN measurement values (85.47%, 8.02%, 6.72%); theoretical values (85.26%, 8.11%, 6.63%)
With tris-(dibenzylideneacetone)dipalladium(0); P(p-CH3OC6H4)3; 5-norbornene-2-carbonitrile; potassium acetate; caesium carbonate; In acetonitrile; at 20 - 80℃; for 15h;Inert atmosphere; Sealed tube; Microwave irradiation;
To a dry 5.0 mL microwave reaction flask equipped with a magnetic stir bar, add Pd2 (dba) 3 (9.2 mg, 0.01 mmol, 0.05 equivalent), tris (4-methoxyphenyl) phosphine (15.5 mg, 0.044 mmol, 0.22 equivalent),Potassium acetate (49 mg, 0.5 mmol, 2.5 equivalents), cesium carbonate (163 mg, 0.5 mmol, 2.5 equivalents), norbornene (38.5 mg, 0.4 mmol, 2.0 equivalents), 1-iodonaphthalene (50.8 mg, 0.2 mmol, 1.0 Equivalent), methyl p-toluenesulfonate (74.5 mg, 0.4 mmol, 2.0 equivalents),Pinacol diborate (152.4 mg, 0.6 mmol, 3.0 equivalents) and dry acetonitrile (2.0 mL). The reaction bottle was capped and sealed and stirred at room temperature for about 5 minutes, after which the mixture was heated to 80 C and stirred for 15 hours. After the reaction vessel was cooled to room temperature, it was filtered through a short silica gel column, rinsed with ethyl acetate (10 mL), and concentrated under vacuum. Purified by column chromatography using petroleum ether: ethyl acetate = 30: 1 (v / v) as eluent to give compound I-30 (white solid, yield 70%).