* 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.
Stage #1: at 80℃; for 2 h; Sealed tube; Green chemistry Stage #2: at 80℃; for 1 h; Sealed tube; Green chemistry
General procedure: A sealed tube equipped with a magnetic stirring bar was charged with styrene 1 (1.0mmol), NBS (2.0 mmol) and water (2.0mL) at room temperature. The resulting mixture was heated to 80 °C for 2h. After disappearance of the reactant (monitored by TLC), reaction mixture was cooled to room temperature. To this reaction mixture molecular iodine (2.2 mmol) and 30percent aq. ammonia solution or n-butylamine (10 mmol) were added and it was heated to 80 °C for 1h. After completion of the reaction (monitored by TLC), saturated Na2S2O3 solution (10 mL) was added to the reaction mixture, and it was extracted with ethyl acetate (2×10 mL). The organic layer was washed with brine solution (10 mL), dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue obtained was purified by column chromatography on 60–120 mesh silica gel using ethyl acetate: n-hexane (1:2) as the eluent to obtain the corresponding aromatic amide 2.
Reference：
[1] Tetrahedron Letters, 2018, vol. 59, # 29, p. 2820 - 2823
[2] Organic and Biomolecular Chemistry, 2017, vol. 15, # 46, p. 9889 - 9894
2
[ 2039-86-3 ]
[ 1878-67-7 ]
Reference：
[1] Advanced Synthesis and Catalysis, 2017, vol. 359, # 12, p. 2132 - 2141
[2] RSC Advances, 2016, vol. 6, # 8, p. 6719 - 6723
3
[ 2039-86-3 ]
[ 2725-82-8 ]
Yield
Reaction Conditions
Operation in experiment
90 %Spectr.
With dimethylamine borane; ReBr2(NO)(CH3CN)(PTA)2 In ethanol at 70℃; for 40 h; Inert atmosphere
General procedure: A solution of the proper olefin substrates (0.5 mmol), dimethylamine-borane (0.25 mmol) and 1 molpercent of the rhenium complex (with 10-15 molpercent of tBuOK according to Table 3) in the given solvent (0.8e1.0 ml) was stirred for given time at 70 °C under nitrogen atmosphere. Upon completion, the reaction mixture was filtered over Celite. The resulting solution was analyzed by 1H NMR spectroscopy. The obtained 1H NMR data of the alkanes were identical to those of the literature [35,49-55]. The yields are listed in Tables 2 and 3.
Reference：
[1] ACS Catalysis, 2016, vol. 6, # 9, p. 6318 - 6323
[2] Journal of the American Chemical Society, 1937, vol. 59, p. 1176
[3] Journal of Organometallic Chemistry, 2011, vol. 696, # 9, p. 1803 - 1808
[4] Journal of Materials Chemistry A, 2015, vol. 3, # 48, p. 24525 - 24531
4
[ 2039-86-3 ]
[ 100-41-4 ]
[ 2725-82-8 ]
Reference：
[1] Journal of the American Chemical Society, 2016, vol. 138, # 19, p. 6107 - 6110
5
[ 2039-86-3 ]
[ 40422-70-6 ]
Reference：
[1] Organic and Biomolecular Chemistry, 2016, vol. 14, # 24, p. 5622 - 5626
6
[ 75-11-6 ]
[ 2039-86-3 ]
[ 1798-85-2 ]
Yield
Reaction Conditions
Operation in experiment
81%
Stage #1: With diethylzinc; 2,4,6-Trichlorophenol In hexanes; dichloromethane at -40℃; for 0.5 h; Stage #2: at 20℃; Stage #3: With potassium permanganate; water In tetrahydrofuran at 0 - 20℃; for 1 h;
1.0 M Diethyl zinc in hexanes (27.3 ml, 27.3 mmol) was added to a solution of 2,4, 6- [TRICHLOROPHENOL] (5.4g, 27.3 mmol) in dichloromethane (100 ml) at-40°C. After stirring for 15 minutes, diiodo-methane (2.2 mL, 27.3 mmol) was added at-40°C and stirred for an additional 15 minutes. 1-Bromo-3-vinyl-benzene (2.5 g, 13.7 mmol) was then added to the reaction mixture, allowed to warm to room temperature, and left stirring overnight. The reaction mixture was diluted with dichloromethane, washed with 1N [HC1] (2X), saturated sodium bicarbonate (2X), saturated sodium sulfite, 1N sodium hydroxide, and saturated brine, dried over magnesium sulfate, filtered and concentrated. GC-MS revealed that the reaction mixture contained [L-BROMO-3-CYCLOPROPYL-BENZENE] and 1-bromo-3-vinyl-benzene. To remove the bromo-3-vinyl-benzene, the crude mixture was reacted with potassium permanganate. A solution of potassium permanganate/water (1.5 g/20 mL) was added drop-wise to a solution of the crude mixture [(-3.] 5 g) in THF (40 mL) at [0°C] and then allowed to warm to room temperature. After 1 hour, the reaction was diluted with diethyl ether, washed with water and saturated brine, dried over anhydrous sodium sulfate filtered and concentrated. Purication by flash column chromatography eluted with 100 hexanes afforded [1-BROMO-3-CYCLOPROPYL-BENZENE] (2.20g, [81percent).] 1.6 M n-Butyllithium in hexanes (3.2 mL, 5.1 mmol) was added drop-wise to a solution of [L-BROMO-3-CYCLOPROPYL-BENZENE] [AT-78°C] and stirred for 1 hour. This reaction mixture was then transferred via canula to a 250 mL round bottom flask equipped with a stirrer bar approximately [1/4 FULL] of solid carbon dioxide and stirred and for 1 hour. The reaction mixture was concentrated and then the residue was diluted with water. The aqueous layer was washed with dichloromethane [(3X),] acidified with 1 N [HC1] to [PH-2,] and extracted with ethyl acetate. The organic phase was washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated to afford 3-cyclopropyl-benzoic (356 mg, 43percent, white [SOLID). IH NMR (DMSO), 6] (ppm): 12.90 (bs, 1H), 7.71 (d, 1H), 7.64 (s, 1H), 7.34 (m, 2H), 2.01 (m, 1H), 0.99 (m, 2H), 0.70 (m, 2H).
Reference：
[1] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1966, p. 218 - 222[2] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1966, # 2, p. 240 - 245
9
[ 2039-86-3 ]
[ 34598-49-7 ]
Reference：
[1] Angewandte Chemie - International Edition, 2015, vol. 54, # 43, p. 12683 - 12686[2] Angew. Chem., 2015, vol. 127, # 43, p. 12874 - 12877,4
10
[ 2039-86-3 ]
[ 28229-69-8 ]
Reference：
[1] Patent: US6063789, 2000, A,
[2] ACS Catalysis, 2017, vol. 7, # 8, p. 5225 - 5233
With dimethylamine borane; ReBr2(NO)(CH3CN)(PTA)2; In ethanol; at 70℃; for 40h;Inert atmosphere;
General procedure: A solution of the proper olefin substrates (0.5 mmol), dimethylamine-borane (0.25 mmol) and 1 mol% of the rhenium complex (with 10-15 mol% of tBuOK according to Table 3) in the given solvent (0.8e1.0 ml) was stirred for given time at 70 C under nitrogen atmosphere. Upon completion, the reaction mixture was filtered over Celite. The resulting solution was analyzed by 1H NMR spectroscopy. The obtained 1H NMR data of the alkanes were identical to those of the literature [35,49-55]. The yields are listed in Tables 2 and 3.
With aluminum (III) chloride; triphenylphosphine; In nitromethane; at 80℃; for 2h;
General procedure: In a typical reaction, alcohol (0.4 mmol) was mixed with AlCl3 (0.02 mmol, 5 mol%) and triphenylphosphine (PPh3, 0.02 mmol, 5 mol%) in nitromethane (1.0 mL). Thereafter the mixture was stirred at 80 C for 2 h. After the reaction, the mixture was cooled to room temperature, and the product was isolated using preparative thin layer chromatography (TLC, eluting solution: petroleum ether/ethyl acetate, 5/1 (v/v)). Tests for substrate scope were all performed with an analogous procedure.
With Rhizomucor miehei lipase; lauric acid; urea hydrogen peroxide adduct; In acetonitrile; at 30℃; for 24h;Enzymatic reaction;
General procedure: Lauric acid (2 mol, 400 mg), RML (50 mg), and finally UHP(1.1 mmol, 104 mg) were added over a solution of the correspondingalkenes 1aeh (1 mmol, 0.66 M) in acetonitrile (1.5 mL).The suspension was shaken at 250 rpm for 24 h at 30 C, and thenthe reaction was quenched by addition of water (1.5 mL). Themixture was extracted with EtOAc (31.5 mL), and an aliquot of thereaction was injected in the GC for the measurement of the conversionvalues.
(E)-2-(3-bromophenyl)ethenesulfonyl chloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
60%
With sulfuryl dichloride; In DMF (N,N-dimethyl-formamide); at 20 - 90℃; for 4.83333h;
[0288] Sulfuryl chloride (2.87 mL, 35.7 mmol) was added dropwise to DMF (3.8 mL) at 0 C. The resulting mixture was stirred at room temperature for 50 min. To the mixture was added <strong>[2039-86-3]3-bromostyrene</strong> (2.7 mL, 21 mmol). The mixture was then heated to 90 C. for 4 h, cooled to room temperature and poured into 50 mL of ice/water. The precipitate was collected by filtration, washed with water (2×), and dried by lyophilization to afford 3.54 g (60%) of the title compound: 1H-NMR (CD3OD) delta 7.55-7.65 (3H, m), 7.38-7.44 (1H, d, m), 7.27 (1H, t, 7.9), 7.16 (1H, d, J=11.3 Hz).
1.0 M Diethyl zinc in hexanes (27.3 ml, 27.3 mmol) was added to a solution of 2,4, 6- [TRICHLOROPHENOL] (5.4g, 27.3 mmol) in dichloromethane (100 ml) at-40C. After stirring for 15 minutes, diiodo-methane (2.2 mL, 27.3 mmol) was added at-40C and stirred for an additional 15 minutes. 1-Bromo-3-vinyl-benzene (2.5 g, 13.7 mmol) was then added to the reaction mixture, allowed to warm to room temperature, and left stirring overnight. The reaction mixture was diluted with dichloromethane, washed with 1N [HC1] (2X), saturated sodium bicarbonate (2X), saturated sodium sulfite, 1N sodium hydroxide, and saturated brine, dried over magnesium sulfate, filtered and concentrated. GC-MS revealed that the reaction mixture contained [L-BROMO-3-CYCLOPROPYL-BENZENE] and 1-bromo-3-vinyl-benzene. To remove the bromo-3-vinyl-benzene, the crude mixture was reacted with potassium permanganate. A solution of potassium permanganate/water (1.5 g/20 mL) was added drop-wise to a solution of the crude mixture [(-3.] 5 g) in THF (40 mL) at [0C] and then allowed to warm to room temperature. After 1 hour, the reaction was diluted with diethyl ether, washed with water and saturated brine, dried over anhydrous sodium sulfate filtered and concentrated. Purication by flash column chromatography eluted with 100 hexanes afforded [1-BROMO-3-CYCLOPROPYL-BENZENE] (2.20g, [81%).] 1.6 M n-Butyllithium in hexanes (3.2 mL, 5.1 mmol) was added drop-wise to a solution of [L-BROMO-3-CYCLOPROPYL-BENZENE] [AT-78C] and stirred for 1 hour. This reaction mixture was then transferred via canula to a 250 mL round bottom flask equipped with a stirrer bar approximately [1/4 FULL] of solid carbon dioxide and stirred and for 1 hour. The reaction mixture was concentrated and then the residue was diluted with water. The aqueous layer was washed with dichloromethane [(3X),] acidified with 1 N [HC1] to [PH-2,] and extracted with ethyl acetate. The organic phase was washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated to afford 3-cyclopropyl-benzoic (356 mg, 43%, white [SOLID). IH NMR (DMSO), 6] (ppm): 12.90 (bs, 1H), 7.71 (d, 1H), 7.64 (s, 1H), 7.34 (m, 2H), 2.01 (m, 1H), 0.99 (m, 2H), 0.70 (m, 2H).
With iodine; copper; In toluene; for 140h;Heating / reflux;
Iodine (0.335 g, 1.32 mmol), diiodomethane (4.3 mL, 53.0 mmol) and 3- bromostyrene (5g, 26.4 mmol) were added successively to a suspension of copper (7.5 g, 118.8 mmol) in toluene (50 mL). The mixture was refluxed for 140h, then filtered and concentrated in vacuo. The residue was distilled under reduced pressure to afford 3-bromo-1-cyclopropylbenzene (0.55g, 10%) as a colorless oil. ¹H NMR (CDC13) 8 : 7.35-7.25 (m, 1 H); 7.25-7.20 (m, 1 H); 7.15-7.05 (m, 1H) ; 7.05- 6.95 (m, 1 H); 1.95-1.85 (m, 1H) ; 1.05-0.95 (m, 2H) ; 0.75-0.65 (m, 2H).
With sodium t-butanolate;tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; In toluene; for 20h;
Example 5; Synthesis of a monomer of:; [0060] A mixture of phenyl(1-naphthyl)amine (10 g, 45.0 mmol), <strong>[2039-86-3]3-bromostyrene</strong> (9.2 g, 50.0 mmol), NaOfBu (5.1 g, 55.0 mmol), Pd2(dba)3 (0.300 g, 0.33 mmol) and P(fBu)3 (0.150 g, 0.74 mmol) was stirred in toluene (80 ml_) under nitrogen for 20 hours. The resulting solution was diluted with diethylether and filtered through celite and silica. Upon evaporation of the solvent a dark brown viscous material was obtained which was purified by chromatography on silica (hexanes) and the desired product was obtained as a white solid (9.8 g, 67%). The product's 1H NMR is shown below.
67%
With sodium t-butanolate;tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; In toluene; for 20h;Inert atmosphere;
A mixture of phenyl(1-naphthyl)amine (10 g, 45.0 mmol), <strong>[2039-86-3]3-bromostyrene</strong> (9.2 g, 50.0 mmol), NaO'Bu (5.1 g, 55.0 mmol), Pd2(dba)3 (0.300 g, 0.33 mmol) and P('Bu)3 (0.150 g, 0.74 mmol) was stirred in toluene (80 mL) under nitrogen for 20 hours. The resulting solution was diluted with diethylether and filtered through celite and silica. Upon evaporation of the solvent a dark brown viscous material was obtained which was purified by chromatography on silica (hexanes) and the desired product was obtained as a white solid (9.8 g, 67%). See FIG. 2.
With sodium hydroxide; dihydrogen peroxide; In tetrahydrofuran; water;
a 3-Bromobenzeneethanol Borane-dimethylsulphide complex (2.0M in THF, 49 ml) was added dropwise to a stirred solution of 3-bromostyrene (10 g, 55 mmol) in THF (130 ml) at 0 C. and the solution was stirred for 3 h at room temperature. 10% Aqueous sodium hydroxide was added cautiously, followed by hydrogen peroxide (30% wt. solution in water, 6 ml) dropwise. After a further 16 h, the mixture was diluted with water, extracted twice with ethyl acetate, the combined extracts washed with saturated sodium bisulphite solution and saturated sodium chloride solution, dried over sodium sulphate and evaporated to give a colourless oil. Purification by flash chromatography, eluding with 30% diethyl ether/hexane gave a colourless oil, [M+Si(CH3)3 derivative]+
With sodium t-butanolate;tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; In toluene; for 20h;Inert atmosphere;
A mixture of diphenylamine (4.6 g, 27.0 mmol), <strong>[2039-86-3]3-bromostyrene</strong> (5.0 g, 27.0 mmol), NaO'Bu (3.0 g, 38.0 mmol), Pd2(dba)3 (0.300 g, 0.33 mmol) and P('Bu)3 (0.150 g, 0.74 mmol) was stirred in toluene (80 mL) under nitrogen for 20 hours. The resulting solution was diluted with diethylether and filtered through celite and silica. Upon evaporation of the solvent a dark brown viscous material was obtained which was purified by chromatography on silica (hexanes) and the desired product was obtained as a white solid (4.25 g, 65% yield). See FIG. 3.
With iodoform; [bis(acetoxy)iodo]benzene; In 1,4-dioxane; at 20℃;Irradiation;
General procedure: A 5 mL oven-dried reaction vessel equipped with a magnetic stirrer bar was charged with styrene (1a, 20.8 mg,0.20 mmol), PhI(OAc)2 (32.1 mg, 50 mol%), CHI3 (2a, 0.20 mmol) and dioxane (2.0 mL). The reaction vessel wasexposed to sunlight at room temperature in air with stirring for 6 h. After completion of the reaction, the mixture wasconcentrated to yield the crude product, which was further purified by flash chromatography (silica gel, petroleumether/ethyl acetate = 10:1 to 5:1) to give the desired product 3a.
With triethylsilane; dichloro[1,1?-bis[bis(1,1-dimethylethyl)phosphino]ferrocene-P,P?]palladium; triethylamine; In 1,4-dioxane; at 100℃; for 0.25h;Inert atmosphere;
General procedure: To a sparge-degassed solution of Et3N (0.405 g, 0.554 mL,4 mmol) and 1,4-dimethoxybenzene (internal standard) (0.138 g, 1 mmol) inanhydrous 1,4-dioxane (12 mL) under a nitrogen atmosphere was added 6-amino-2-chloro-5-fluoronicotinonitrile (343 mg, 2 mmol), [(1,10-bis-(di-tertbutyl-phosphino)ferrocene)PdCl2] (64 mg, 0.1 mmol) and Et3SiH (1.160 g,1.592 mL, 10 mmol). The mixture was then heated to 100 C with stirring.The reaction was monitored using 1H NMR spectroscopy, taking aliquots of thecrude reaction mixture. Upon completion, the mixture was diluted with CH2Cl2(20 mL) and washed with H2O (1 20 mL). The aqueous layer was thenextracted with CH2Cl2 (2 20 mL). The combined organics were dried overanhydrous MgSO4, filtered, and the solvent was removed under reducedpressure to leave the crude reaction product. The crude product was purifiedby flash silica chromatography with 0-5% methanolic NH3 (7 M) in CH2Cl2 asthe eluent. The solvent was then removed from fractions containing thedesired product to leave 6-amino-5-fluoronicotinonitrile (3) (148 mg,1.076 mmol).
With tris(2,2'-bipyridyl)ruthenium dichloride; Bromoform; [bis(acetoxy)iodo]benzene; In 1,4-dioxane; at 20℃; for 8h;Irradiation;
General procedure: Under conditions B: A 5 mL oven-dried reaction vessel equipped with a magnetic stirrer bar was charged withstyrene (1a, 20.8 mg, 0.20 mmol), Ru(bpy)3Cl2 (1.28 mg, 0.002 mmol, 1.0 mol%), PhI(OAc)2 (64.0 mg, 1.0 equiv.),CHBr3 (2b, 0.20 mmol) and dioxane (2.0 mL). The reaction vessel was exposed to blue LED (450-455 nm, 3 W) atroom temperature in air with stirring for 8 h. After completion of the reaction, the mixture was concentrated to yieldthe crude product, which was further purified by flash chromatography (silica gel, petroleum ether/ethyl acetate =10:1 to 5:1) to give the desired product 4a.
With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione; water; at 80℃; for 3h;
General procedure: To a mixture of olefin (0.5 mmol) and tween-80 (30 mL) in water (3 mL) was added DBH (214.5 mg, 0.75 mmol) at room temperature, and the mixture was stirred under the conditions as indicated in Table 1. After cooling to room temperature and removal of solvent under reduced pressure, EtOH (3 mL), thiourea (57.1 mg, 0.75 mmol) (or 0.75 mmol of N-methylthiourea/N-phenethylthiourea) were added to the mixture, and the obtained mixture was stirred for 2 h at 80 C. The mixture was diluted with ethyl acetate (60 mL). The organic phase was washed with brine (10mL x 3) and dried over Na2SO4. After concentrated under reduced pressure, the residue was purified by preparative thin layer chromatography to afford the corresponding 2-aminothiazoles.
With formic acid; sodium nitrite; In acetonitrile; at 70℃; for 4h;Schlenk technique;
General procedure: A Schlenk tube was charged with olefins 1 (0.4 mmol), NaNO2 (138 mg, 2 mmol), HCOOH (0.5 mL, 10 mmol), and CH3CN(4.5mL). The reaction mixture was stirred at 70 C under air atmosphere for 4 h. After cooling to room temperature, the solution was filtered to remove the solid by-product then was washed with ethyl acetate (3×10 mL). The solution was concentrated under vacuum and purified by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate) to obtain the desired product 2.
84.26%
With formic acid; 5,10,15,20?tetrakis?(4?sulfonatophenyl)?porphyrin?iron(III) chloride; sodium nitrite; In acetonitrile; at 70℃; for 4.5h;
In the reaction tube was added 0.4 mmol of m-bromostyrene, 2 mmol of sodium nitrite,5 mg of metallic iron (III) porphyrin, 4.5 ml of acetonitrile solvent, heated and stirred at 70 C in an air atmosphere,0.5 ml of formic acid was added dropwise within the first 0.5 hours, after reacting for 4 hours, heating and stirring were stopped,After cooling to room temperature, the crude product was obtained by rotary evaporator and then purified by column chromatography,The target product was obtained. The column eluant used was a mixed solvent of petroleum ether and ethyl acetate.The structure of m-bromobenzonitrile is shown below:The compound is a white solid with a yield of 84.26% and its nuclear magnetic data as follows:
With potassium iodide; In tetrahydrofuran; water; at 30℃;Electrochemical reaction;
General procedure: An undivided cell was equipped with a carbon plate anode (5 cm2) and a Fe plate cathode (5cm2) and connected to a DC regulated power supply. The solution of sulfonyl hydrazide 1a-1f (300mg, 1.01-1.61mmol), alkene 2a-2p (1.93-3.22mmol, molar ratio 1.2 or 2mol 2/mol 1) and supporting electrolyte KI (2.02-3.22mmol, molar ratio 2mol/mol 1) in 30mL of THF-H2O (1:1) was electrolyzed using constant current conditions (60 or 270mA/cm2) at 30C, under magnetic stirring. During electrosynthesis the reaction mixture is cooled externally. Then electrodes were washed with EtOH (2×30mL). The solvent from combined organic phases was removed under reduced pressure. The residue was diluted with EtOAc (50mL) and washed with saturated aqueous solution of Na2S2O3 (8mL), brine (2×8mL) and water (2×8mL), dried over Na2SO4, concentrated under reduced pressure and dried at 10-20 torr. The desired products 3aa-3fa, 3ab-3ap were isolated by chromatography on SiO2 with elution using PE-EA in a linear gradient of the latter from 10 to 50vol%. The yield when the reaction was performed with current density 270mA/cm2 is reported in the parentheses.
With tetrakis(actonitrile)copper(I) hexafluorophosphate; 1,8-diazabicyclo[5.4.0]undec-7-ene; In N,N-dimethyl-formamide; at 60℃; for 2h;
General procedure: Into a solution of 4-vinylbiphenyl (90 mg, 0.5 mmol) in DMF (1 mL) was added Togni?s reagent (415 mg, 1.25 mmol) and DBU (152 mg, 1 mmol), followed by [(MeCN)4Cu]PF6 (37 mg, 0.1 mmol). The reaction mixture was stirred at 60 C for 2 h. After being cooled to room temperature, the mixture was subjected to column chromatography to afford pure product 2a.
With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; In 1,4-dioxane; at 80℃; for 1h;Green chemistry;
General procedure: A mixture of styrene (0.104 g, 1.0 mmol), Claycop [0.605 g, 1.5 mmol containing 1.5 equiv Cu(NO3)2], TEMPO (0.0156 g, 20 mol%), and 1,4-dioxane (5 mL) was stirred at 80 C for 1 h. The mixture was then cooled to r.t., and the Claycop was collected by filtration and washed with 1,4-dioxane (3 × 5 mL). The organic phases were combined and concentrated under vacuum. The crude product was purified by recrystallization or column chromatography (EtOAc-hexanes) to give a crystalline yellow solid
82%
With 2,2,6,6-tetramethyl-piperidine-N-oxyl; dipotassium peroxodisulfate; sodium nitrite; In 1,2-dichloro-ethane; at 100℃; for 24h;Sealed tube;
General procedure: To a 25 mL sealed tube were added alkenes 1 or 3 (0.5mmol) with NaNO2 (1.5 equiv.), K2S2O8 (2.0 equiv.), TEMPO (1.2 equiv.) and ClCH2CH2Cl (2 mL). The reaction mixture was stirred at 100 oC for 24 h. After the reaction was finished, the reaction was cooled to room temperature. Dichloromethane (2 mL) and water (5 mL) were added. The organic layer was separated, and the aqueous phase was extracted with dichloromethane (5 mL × 3). The combined organic layers were dried with anhydrous Na2SO4, filtered. After evaporating the solvent in vacuum, the residue was purified by column chromatography eluting with PE/EtOAc to obtain the pure nitroalkenes 2 or 4.
In a glove box, in a reaction flask,(NiPr) N (SiMe3) iPr] Eu} 2 (0.01 mmol, 0.0124 g) was added in a constant proportion to the catalyst [iPr (Me3Si) NC (NiPr) N (CH2)Then diphenylphosphine (0.174 mL, 1 mmol) was added with a syringe and then stirred at room temperature for 10 min,A mixture of m-bromostyrene (0.130 mL,1 mmol), 60 reaction 6h,Use a dropper to draw a drop in the nuclear tube, add CD to the solution.The calculated 1H spectrum yield was 94% and the remaining liquid was dissolved with an appropriate amount of ethyl acetate,The solvent was removed by rotary distillation and the solid was separated on silica gel column using ethyl acetate / petroleum ether as eluant to give the corresponding alkyl phosphines, 3-Br-C6H4CH2CH2PPh2, 0.2433 g, yield 66%.
With (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)CuBr; In dimethyl sulfoxide; at 20℃; for 0.5h;Inert atmosphere;
General procedure: General procedure A: To a dried glass tube, Togni reagent 2 (99mg, 0.3mmol, 1.5equiv), (L3)CuBr (10mg, 0.02mmol, 0.1equiv) and DMSO (1.0mL) were added under N2 atmosphere, followed by substrate 1 (0.2mmol, 1.0equiv) and TMSCN (54muL, 0.4mmol, 2.0equiv). After the reaction mixture was stirred at room temperature for 0.5h, dichloromethane was added and the mixture was filtered through a short pad of celite. The filtrate was washed with water (15mL×3) and dried over anhydride Na2SO4. After the removal of solvent, the residue was purified by column chromatography on silica gel with a gradient eluent of petroleum ether and ethyl acetate to afford the product. General procedure A: Pale yellow liquid; 51.7mg, 93%; 1H NMR (400MHz, CDCl3): delta 7.56-7.50 (m, 2H), 7.35-7.28 (m, 2H), 4.07 (dd, J=9.6, 5.6Hz, 1H), 2.90-2.76 (m, 1H), 2.66-2.53 (m, 1H); 13C NMR (100MHz, CDCl3): delta 135.4, 132.3, 131.1, 130.3, 125.9, 124.4 (q, J=276.4Hz), 123.4, 117.9, 39.8 (q, J=31.1Hz), 30.8 (q, J=3.1Hz); 19F NMR (376MHz, CDCl3): delta -62.5 (t, J=9.8Hz); HRMS (EI), calcd. for C10H7BrF3N 276.9714 [M]+, found 276.9710.
With oxygen; benzoic acid; sodium nitrite; In toluene; at 80℃; for 30h;
General procedure: To a solution of alkene (0.3 mmol) and benzoic acid (0.15 mmol ) in toluene (1 mL) was added NaNO2 (0.45 mmol) under an air atmosphere and the mixture was stirred at 80 oC for 20-30 h. The reaction mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (eluent: EtOAc/PE = 1:8) to yield the corresponding product 2.
2-(2-(3-bromophenyl)-2-hydroxyethoxy)isoindoline-1,3-dione[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
84%
With tert.-butylhydroperoxide; oxygen; In decane; 1,2-dichloro-ethane; at 20℃; under 760.051 Torr; for 80h;
General procedure: To a solution of N-hydroxyphthalimide (2, 0.3 mmol, 48.9 mg) in DCE (3.0 mL) was added styrene (1a, 0.6 mmol), 10% TBHP (5-6 M in decane). The flask was evacuated and back filled with O2 for three times. The reaction mixture was then stirred for 24 h at room temperature. After the reaction, the resulting mixture was quenched with water and extracted twice with EtOAc. The combined organic extracts were washed with brine, dried over Na2SO4 and concentrated. Purification of the crude product by flash column chromatography afforded the product 3a (petroleum ether/ethyl acetate as eluent (6:1)).
1-(3-bromophenyl)-2-nitroethan-1-one oxime[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
68%
With tert.-butylnitrite; water; In dimethyl sulfoxide; at 50℃; for 1.5h;Inert atmosphere; Schlenk technique;
General procedure: 1a (0.25 mmol) and TBN (0.50 mmol) were respectively added to the solvent of DMSO and water (v : v = 20:1, 1.0 ml) or DMF and water (v : v = 20:1, 1.0 ml) in a Schlenk tube. The tube was vacuumized and degassed with nitrogen for several times. The mixture was then stirred at 50 C for 1.5 h. When the reaction was finished, appropriate ethyl acetate was added to the mixture and DMSO or DMF were extracted by water. The obtained organic phase was evaporated to remove the solvent and the resulting residue was further purified by flash column chromatography using petroleum ether/ethyl acetate (v : v = 3:1) to afford the product 2a.
52%
With tert.-butylnitrite; In water; dimethyl sulfoxide; at 20℃; for 12h;
General procedure: To a 25 mL round bottom flask charged with a magnetic stir-bar was added H2O (0.5 mL),Styrene (0.5 mmol), tert-butyl nitrite (1 mmol) and DMSO (1 mL).Then the reaction mixture wasstirred at room temperature for 12h. After the reaction was finished, the mixture was diluted withCH2Cl2, washed with brine and extracted with CH2Cl2. The combined organic extracts were driedover Na2SO4, concentrated in vacuum, and the resulting residue was purified by silica gel columnchromatography (petroleum ether/ethyl acetate=5:1) to afford the desired product. The Z/E ratioswere determined from the signals of CH2 groups connected to the nitro group.
1-bromo-3-(1,2-dithiocyanatoethyl)benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
76%
With Selectfluor; copper(I) bromide; In dichloromethane; at 90℃; for 3h;Sealed tube;
General procedure: To a solution of the styrene 1a (31.2 mg, 0.3 mmol) in CH2Cl2 (3.0 ml) was added the NH4SCN2 (45.7 mg, 0.6 mmol), Selectfluor (212.6 mg, 0.6 mmol), and CuBr (4.3 mg, 0.03 mmol) in a sealed tube. The sealed tube was then tightly sealed with a screw cap and the reaction was stirred for the 3.0 h at 90 C. After the reaction finished, the reaction mixture was cooled to room temperature. The mixture was extracted with CH2Cl2 (3 × 5.0 mL), the combined organic phases were dried over anhydrous Na2SO4 and the solvent was evaporated under vacuum. The residue was purified by column chromatography to give the corresponding products 3a (53.5 mg, 81%).
With potassium carbonate; In 1,4-dioxane; water; at 100℃; for 12h;Inert atmosphere;
Bromobenzaldehyde 4a (10 g, 54.05 mmol) was dissolved in a mixed solvent of 102 mL of dioxane and water (v / v = 50: 1), potassium carbonate (18.64 g, 135 mmol) and methyltriphenylphosphonium iodide (43.70g, 108.11 mmol),The temperature was raised to 100 C and the reaction was stirred for 12 hours. Filtered and the filter cake was washed with 200 mL of n-hexane and ethyl acetate (V / V = 50: 1) mixed solvent. 1-bromo-3-vinylbenzene 4b (10 g, yellow liquid), yield: 100.0%.
With [bis(acetoxy)iodo]benzene; copper(l) chloride; In 1,2-dichloro-ethane; at 80℃; for 12h;
General procedure: 4.1.1. Typical procedure for the synthesis of products 3. To a solutionof N-hydroxyphthalimide (2, 0.66 mmol, 107.6 mg) in DCE (2.0 mL)was added styrene (1, 0.3 mmol), CuCl (10%, 0.03 mmol, 3.0 mg),PhI(OAc)2 (212.5 mg, 2.2 equiv, 0.66 mmol). The reaction mixturewas then stirred for 12 h at 80 C in air. After the reaction, the resulting mixture was quenched with water and extracted twicewith EtOAc (10 mL). The combined organic extracts were washedwith brine (10 mL), dried over Na2SO4 and concentrated. Purica-tion of the crude product by ash column chromatography affordedthe product 3 (petroleum ether/ethyl acetate as eluent (6:1)).
With sodium hydroxide; In ethanol; at 0 - 20℃; for 12h;
3000 mL 3-neck round bottom flask was charged with 3-bromo-benzaldehyde 106.31 g (575 mmol) and 2,3-dihydro-indene -1-one 80g (5472 mmol) and the mixture of ethanol and then dissolved in 1280 mLFrom 0 slowly into a sodium hydroxide 27.36 g (6840 mmol) was stirred at room temperature for 12 hours. The precipitated solid was cooled by vacuum filtration and washed with methanol to a light yellow solid compound 144 g: (yield: 84%).
2,2-dibromo-1-(3-bromophenyl)ethan-1-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81%
With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione; In 1,2-dimethoxyethane; water; at 80℃; for 4h;
General procedure: DBH (429 mg, 1.5 mmol) was added into the mixture of olefin (0.5 mmol) in DME-water (1.35 mL : 0.3 mL) at rt. The resultant mixture was heated to 80 C and stirred for 4 h (for 2b, 4 h (at) 70 C; for 2c, 5 h (at) 80 C; and 2j, 2.5 h (at) 75 C). After the reaction was completed, the mixture was quenched by saturated sodium bicarbonate (1 mL). Then, the reaction mixture was extracted by ethyl acetate, washed by brine, and dried over Na2SO4 subsequently. After concentrated in vacuo, the crude product was purified by prepared thin layer chromatography to give the pure product. All alpha,alpha-dibromoketones (except for 2b and 2c) obtained here are known compounds and corresponding references are listed at the end of this part.
With dihydrogen peroxide; In water; acetonitrile; at 55℃; for 12h;
General procedure: With the dissolution of substrate (0.4 mmol) in CH 3 CN (2 mL), Pd0/RGO (0.01 g), H 2 O (0.5 mL), and GO (0.01 g) were orderly added into apressure bottle (35 mL). The mixture was dispersed by ultrasound forabout 30 min at 25 C. Then H 2 O 2 (30 wt%, 4 mmol) was cautiously added dropwise. Immediately, the reaction system was heated to 55 Cwith lid closed until the process was fully completed (detected by TLC).Subsequently, Pd0/RGO and GO were removed by centrifuge. Themixture was extracted by deionized water and ethyl acetate. After thelayers were separated, the organic part was washed with deionizedwater, dried with anhydrous NaSO 4 , ltered and evaporated by reducedpressure distillation. Finally, purication of the crude product wascarried out by column chromatography. For 14, 18, 24, 40 (Table 2),excess hydrogen peroxide was added after half of the total reaction time.
ethyl 5-(3-bromophenyl)-4,5-dihydroisoxazole-3-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
77%
With 1,4-diaza-bicyclo[2.2.2]octane; tert.-butylnitrite; copper(II) acetate monohydrate; In toluene; at 80℃; for 0.12h;Sealed tube;
The reaction flask was charged with Cu (OAc) 2.H2O (10 mol%), DABCO (3 mmol), toluene 15 mL, compound 1 l(3 mmol), compound 2a (6 mmol), t-butyl nitrite 3 (6 mmol), and then the system was sealed at 80 CAfter heating for about 12 hours, the mixture was extracted with ethyl acetate (20 mL x 3), washed three times with saturated brine, dried over anhydrous sodium sulfateThe organic layer was purified by a simple column chromatography to give the product 4l in a yield of 77%.
General procedure: A sealed tube equipped with a magnetic stirring bar was charged with styrene 1 (1.0mmol), NBS (2.0 mmol) and water (2.0mL) at room temperature. The resulting mixture was heated to 80 C for 2h. After disappearance of the reactant (monitored by TLC), reaction mixture was cooled to room temperature. To this reaction mixture molecular iodine (2.2 mmol) and 30% aq. ammonia solution or n-butylamine (10 mmol) were added and it was heated to 80 C for 1h. After completion of the reaction (monitored by TLC), saturated Na2S2O3 solution (10 mL) was added to the reaction mixture, and it was extracted with ethyl acetate (2×10 mL). The organic layer was washed with brine solution (10 mL), dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue obtained was purified by column chromatography on 60-120 mesh silica gel using ethyl acetate: n-hexane (1:2) as the eluent to obtain the corresponding aromatic amide 2.
With dipotassium peroxodisulfate; potassium iodide; In acetonitrile; at 20℃; for 12h;
General procedure: Styrene 1a (0.3 mmol), 4-methyl benzene sulfonyl hydrazine 2a (0.6 mmol), diphenyl diselenide (0.3 mmol), K2S2O8 (0.6 mmol), KI (0.2 equiv.), and CH3CN (2.0 mL) at 20 C for 12 h (monitored by thin-layer chromatography (TLC)), quenched with water, extracted with dichloromethane (5×3 mL), and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the residue was purified by a shot flash silica gel column chromatography (EtOAc/petro ether=1:8)to give compound 3a as a white solid (111.1 mg, 89%).
(S)-2-(3-bromophenyl)-2-methyl-4-phenylpent-4-enal[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
74%
With tetrakis(triphenylphosphine) palladium(0); (R)-3,3'-bis(2,4,6-triisopropylphenyl)binol phosphoric acid; dicarbonyl(acetylacotonato)rhodium(I); 1,2-bis(2,5-diphenylphospholano)ethane; hydrogen; 2-phenyl-2-propylamine; In tert-butyl methyl ether; toluene; at 40℃; under 750.075 Torr; for 48h;Schlenk technique; Molecular sieve;
General procedure: To a flame-dried, nitrogen-filled Schlenk tube equipped with a stir bar were added alkene 1 (20.8 mg, 0.2 mmol), allylic alcohol 2 (0.4 mmol, 2.0 equiv), 2-phenylpropan-2-amine (5.4-27.0 mg, 0.2-1.0 equiv), Rh(acac)(CO)2 (0.52 mg, 0.002 mmol, 0.01 equiv), Pd(Ph3P)4 (6.9 mg, 0.006 mmol, 0.03 equiv), (R)-TRIP (15.1 mg, 0.02 mmol, 0.1 equiv), a 3 Amolecular sieve (150 mg). Then, rac-Ph-BPE (0.0024 mmol, 0.012 equiv) in 0.25 mL of toluene and 2.0 mL of tert-butyl methyl ether were added under nitrogen. After that, oxygen was removed by a freeze pump-thaw process three times. The Schlenk tube was refilled with 1 bar of syngas (CO:H2 = 1:1). After being stirred at 40C for 48 hr, the vial was cooled down to room temperature, and the reaction mixture was acidified with 2 N HCl (2 mL) at room temperature for 30 min and extracted with ethyl ether (4 3 5 mL). The combined organic layers were dried over anhydrous Na2SO4. The mixture was filtered and concentrated in vacuo. The residue was purified through flash column chromatography (SiO2, hexanes/acetonitrile = 8/1) to provide product 3.
1-(3-bromophenyl)-2-diphenylphosphorylethyl nitrate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81%
With ammonium cerium (IV) nitrate; In 1,4-dioxane; at 40℃;Schlenk technique; Inert atmosphere;
Phosphorus diphenyloxide (40.4 mg, 0.2 mmol) and ceric ammonium nitrate (219 mg, 0.4 mmol) were added to a Schlenk tube equipped with a magnet stirrer, nitrogen gas was repeatedly replaced using a double-row tube, and the entire system was placed under a nitrogen atmosphere. ,Then <strong>[2039-86-3]3-bromostyrene</strong> (36 mg, 0.5 mmol) and 2 mL of 1,4-dioxane were added to the system and the reaction was carried out at 40C. The reaction was followed by TLC until the reaction was complete.After the reaction was completed, the reaction solution was concentrated and a 3:1 volume ratio of petroleum ether and ethyl acetate was used as an eluent. The product was separated by column chromatography to obtain 1-(3-bromophenyl)-2-diphenylphosphorylethyl nitrate, yield 81%.
2-(2-(3-bromophenyl)-2-iodoethoxy)isoindoline-1,3-dione[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
79%
With [bis(acetoxy)iodo]benzene; iodine; In dichloromethane; at 20 - 25℃; for 0.166667h;
General procedure: Iodine (64 mg, 0.25 mmol) was added to a stirred mixture of vinylarene 1a-k (52-97 mg,0.50 mmol) and N-hydroxyimide 2a,b (58-82 mg, 0.50 mmol) in DCM (3 mL) at 20-25. Then, PhI(OAc)2 (97 mg, 0.30 mmol) was added. In the additional experiments compounds 3ca and 3ga were prepared using IBX (140 mg, 0.50 mmol) or DMP (64 mg,0.15 mmol) instead of PhI(OAc)2. After stirring for 10 min under air atmosphere at 20-25 DCM (30 mL) was added and the mixture was washed with aqueous solution of Na2S2O3·5H2O (200 mg in 20 mL of water), saturated aqueous NaHCO3 solution (20mL), then with water (20 mL), dried over anhydrous MgSO4 and filtered. DCM wasrotary evaporated at 20-25 under water-jet vacuum (20-30 mmHg). Products 3aa-ka, 3ab-db, 3fb, 3hb and 3kb were isolated by column chromatography on silica gel usingwith EtOAc - DCM eluent (with the volume part of EtOAc gradually increased from 0%to 2.5%).Iodo-oxyimides 3aa-ka, 3ab-db, 3fb, 3hb and 3kb were stored in the freezer and handled with minimal heat due to their potential instability at elevated temperature, whichwas indicated by the darkening both pure powders and solutions when standing at roomtemperature for even a few hours.
77%
With tert.-butylhydroperoxide; iodine; In 1,2-dichloro-ethane; at 80℃; for 6h;
General procedure: Alkenes (1.5 mmol) and TBHP (0.6 mmol) was added to a solutionof N-hydroxyphthalimide (0.3 mmol) and iodide (0.15mmol) in 2 mL of DCE. After the reaction mixture was stirred at80 C for 6 h, the solvent was removed under reduced pressure,and the residual was treated with silica gel chromatography togive compounds.
71%
With ammonium cerium (IV) nitrate; iodine; In dichloromethane; water; at 20 - 25℃; for 0.5h;
General procedure: Iodine (127 mg, 0.5 mmol) was added to a stirred mixture of vinyl substrate 1a-i (172-366 mg, 2.0 mmol) and N-hydroxyphthalimide 2 (163 mg, 1.0 mmol) in DCM/H2O (6.0 mL, 2:1 v/v) at 20-25 C. Then, CAN (822 mg, 1.5 mmol) was added. After stirring the reaction mixture under air atmosphere at 20-25 C for 30 min, DCM (30 mL) was added and the mixture was washed with aqueous solution of Na2S2O3*5H2O (200 mg in 20 mL of water), saturated aqueous NaHCO3 solution (20 mL), then with water (20 mL), dried over anhydrous Na2SO4 and filtered. DCM was rotary evaporated at 20-25 C under reduced pressure (20-30 mmHg) Products 6a-i were isolated by column chromatography on silica gel using DCM/EtOAc as eluent (with the volume part of EtOAc gradually increased from 0% to 5%).
With tris(bipyridine)ruthenium(II) dichloride hexahydrate; potassium carbonate; triphenylphosphine; In acetonitrile; at 20℃; for 4h;Schlenk technique; Inert atmosphere; Irradiation;
In a Schlenk tube equipped with a magnetic stirrer, 163.2 mg of K2CO3 (1.5:1 molar ratio to m-bromobenzyl bromide) was added, and 314.4 mg of triphenylphosphine (molar ratio to m-bromobenzyl bromide was 1.5:1), 3.8 mg Ru(bpy)3Cl2-6H2O (molar ratio to m-bromobenzyl bromide is 0.005:1), 60 mg paraformaldehyde, 10 mL acetonitrile, 248 mg 3-bromobenzyl bromide, argon gas for 5 minutes Under visible light, normal temperature, reaction time is 4h,The product was isolated and purified by petroleum ether to give 162 mg of 3-bromostyrene (formula 4) in a yield of 89%.
With silica gel; phosphorus tribromide; In dichloromethane; at 20℃; for 0.75h;
General procedure: Into a round-bottom flask containing a magnetic stirring bar was added styrene (1.0 eq.), SiO2 gel (230-400 mesh; 0.5 g/mmol styrene) and DCM (2.5 mL/mmol styrene). The mixture was stirred vigorously, and 0.4 eq. PBr3 (0.4 M in DCM) was added in one portion, resulting in a deep orange or red solution. The reaction was stirred for 30-60 minutes and monitored by TLC. When the reaction appeared complete by TLC, 10% NaHCO3 was added dropwise to the reaction until the solution became colourless or light yellow, and no further evolution of CO2 was noted. The resulting slurry was filtered through a celite plug and eluted with DCM. The resulting organic solution was evaporated to dryness to afford the hydrobromination product 8a.
With copper(l) iodide; 1,10-Phenanthroline; 1,8-diazabicyclo[5.4.0]undec-7-ene; In acetonitrile; at 110℃; for 1.5h;Sealed tube; Green chemistry;
First, a stirrer was placed in a 35 mL sealed tube, and 40 muL of <strong>[2039-86-3]3-bromostyrene</strong> (0.3 mmol), 1.0 ml of acetonitrile, and 38 muL of bromoacetonitrile (0.60 mmol) were added thereto, and the mixture was mixed. Add 5.4 mg of Phen (0.03 mmol), 5.7 mg of Cul (0·03 mmol) and 91 muL of DBU (0 · 60 mmol), seal the tube tightly with a cock, heat to 110 C, stir for 1.5 hours, after the reaction is over, the system is cooled to 2 ml of distilled water was added to the reaction system at room temperature, extracted with ethyl acetate, and the organic phase was combined, and the solvent of the organic phase was distilled off under reduced pressure.50.6 mg of a colorless liquid product 3e was obtained by silica gel column chromatography.The yield was 76%.
2-(1-(3-bromophenyl)-2-hydroxyethyl)naphthalene-1,4-dione[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
75%
With ammonium peroxydisulfate; water; copper(ll) bromide; In acetone; acetonitrile; at 110℃; for 4h;Sealed tube;
General procedure: To a mixture of H2O (0.7 mL), acetone (0.7 mL) and acetonitrile (0.7 mL) in a seal tube was added 1 (0.3 mmol), 6 (0.1 mmol), CuBr2 (0.03 mmol), and (NH4)2S2O8 (0.2mmol) at room temperature. The resulting mixture was stirred at 110 C for 4 h. Then the reaction was cooled to room temperature and extracted with ethyl acetate. Organic layers were combined and dried with MgSO4. Solvent was evaporated under reduced pressure and the residue was purified by flash chromatography using ethylacetate/petroleum ether as eluent to give the desired product.
With 10% Mobeta zeolite; In neat (no solvent); at 70℃; for 6h;Sealed tube;
General procedure: 10% Mobeta zeolite (100 mg) was introduced to the well stirred solution of vinylarene (1 mmol) and alcohol (0.8 mmol) in a 15 ml of sealed vial and the reaction mixture was allowed to stir at 70 C. After disappearance of the substrate (monitored by TLC) or after an appropriate time, the reaction mixture was cooled to room temperature, diluted with ethyl acetate. The catalyst was removed by filtration, rinsed with ethyl acetate and removal of solvent in vacuo yielded a crude residue. The crude residue was further purified by column chromatography on silica gel (230-400 mesh) using ethyl acetate/hexane as eluent to afford pure products. All the products were identified on the basis of NMR spectral data and quantified using gas chromatography. More details on catalyst characterization and analytical procedures are provided in supporting information.
3-(3-bromophenyl)-4,5-diphenyl-2,3-dihydroselenophene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
97%
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; (S,S)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane In toluene at 100℃; for 2h;
Preparation of 3-(3-bromophenyl)-4,5-diphenyl-2,3-dihydroselenophene
[Rh(COD)Cl]2 (4.93 mg, 0.01 mmol) and (S,S)-DIOP (12.0 mg, 0.024 mmol) in toluene solvent (1 mL),After adding 4,5-diphenyl-1,2,3-selenadiazole (57.04 mg, 0.2 mmol) and 1-bromo-3-vinylbenzene (0.078 mL, 0.6 mmol), react at 100 oC for 2 hours. After completion of the reaction, the solvent is removed using an evaporator. And the column (Ether: Hexane = 1: 50) to proceed to obtain the desired compound 3-(3-bromophenyl)-4,5-diphenyl-2,3-dihydroselenophene (85.4 mg, 97%).
97%
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; (S,S)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane In toluene at 100℃; for 2h;
2 Preparation of 3-(3-Bromophenyl)-4,5-diphenyl-2,3-dihydroselenophene
[Rh(COD)Cl]2(4.93 mg, 0.01 mmol) and (S,S)-DIOP (12.0 mg, 0.024 mmol) in toluene solvent (1 mL),4,5-diphenyl-1,2,3-selenadiazole (57.04 mg, 0.2 mmol), 1-bromo-3-vinylbenzene (0.078 mL, 0.6 mmol)After adding, it was reacted at 100oC for 2 hours. After completion of the reaction, the solvent is removed using an evaporator. Then proceed to the column (Ether: Hexane = 1: 50),3-(3-bromophenyl)-4,5-diphenyl-2,3-dihydroselenophene (85.4 mg, 97%) was obtained.
83%
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; (S,S)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane In toluene at 100℃; for 2h;
Preparation of 3-(3-bromophenyl)-4,5-diphenyl-2,3-dihydroselenophene
In toluene solvent (1 mL)[Rh (COD) Cl] 2 (4.93 mg, 0.01 mmol) and (S, S) -DIOP (12.0 mg, 0.024 mmol), 4,5-diphenyl-1,2,3-selenadiazole (57.04 mg, 0.2 mmol ), 1-bromo-3-vinylbenzene (0.078 mL, 0.6 mmol) is added, followed by reaction at 100 oC for 2 hours. After the reaction is completed, the solvent is removed using an evaporator. Then proceed to the column (Ether: Hexane = 1: 50) to the desired compound3-(3-bromophenyl)-4,5-diphenyl-2,3-dihydroselenophene (85.4 mg, 97%) was obtained.
With tris(2,2'-bipyridyl)ruthenium dichloride; chloroform; [bis(acetoxy)iodo]benzene; In chloroform; at 20℃; for 12h;Irradiation;
General procedure: A 5 mL oven-dried reaction vessel equipped with a magnetic stirrer bar was charged with styrene (1a, 20.8 mg,0.20 mmol), Ru(bpy)3Cl2 (1.92 mg, 0.003 mmol, 1.5 mol%), PhI(OAc)2 (64.4 mg, 0.20 mmol, 1.0 equiv.) and CHCl3(2c, 2.0 mL). The reaction vessel was exposed to blue LED (450-455 nm, 3 W) at room temperature in air withstirring for 12 h. After completion of the reaction, the mixture was concentrated to yield the crude product, which wasfurther purified by flash chromatography (silica gel, petroleum ether/ethyl acetate = 10:1 to 5:1) to give the desiredproduct 5a.
2-iodo-1-(3-bromophenyl)ethyl diphenylphosphinate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92%
With N-iodo-succinimide; In tetrahydrofuran; at 40℃; for 12h;Inert atmosphere;
0.5 mmol of diphenylphosphinic acid,0.5 mmol of <strong>[2039-86-3]3-bromostyrene</strong> and 0.6 mmol of N-iodosuccinimide were added to the Schlenk tube under a nitrogen atmosphere.Add 1.0 mL of tetrahydrofuran under a nitrogen atmosphere and stir the reaction at 40 oC for 12 hours.After the reaction is completed, the target product can be obtained in 92% yield by column chromatography.
2,2'-(1-(3-bromophenyl)ethane-1,2-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
99%
With C37H60N2OPtSi2; In n-heptane; at 20℃; for 20h;Schlenk technique; Inert atmosphere;
General procedure: A screw cap vial equipped with magnetic stir bar was charged with freshly distilled alkene (1 mmol) and bis(pinacolato)diboron B2Pin2 (1.1 mmol) followed by 4 ml of heptane. (7-Dipp)Pt(dvtms) (4 mg) of was added and the reaction mixture was allowed to stir at room temperature for 20h before evaporated to dryness. The residue was purified by column chromatography (EtOAc/hexanes as eluent).
In a clean and dry round-bottomed flask, add 36 mg of m-bromostyrene and 29 mg of p-toluenethiol, and then add 2 mL of toluene. Slowly add 46 mg of trimethyliodosilane at room temperature. Stir the reaction for no more than 15 minutes. Finally pass through the column. Chromatographic separation gave a clear liquid product. The liquid was subjected to nuclear magnetic resonance proton spectroscopy and carbon spectroscopy analysis to determine the corresponding thioether compound II with a yield of 90%. The nuclear magnetic resonance proton spectroscopy and carbon spectroscopy analysis results are shown in Figures 3 to 4, respectively.
With [bis(acetoxy)iodo]benzene; In tetrahydrofuran; at 80℃; for 16h;Sealed tube;
General procedure: A mixture of styrene (1, 0.2 mmol), sulfonyl chloride (2,0.4 mmol), PhI(OOCPh)2 (0.4 mmol) were added into a vial containing a stirring bar and sealed with a Teflon-lined cap. Then THF (2 mL) was introduced. The resulting mixture was stirred at 80 C for 16 h. Then the mixture was added into H2O (25 mL) and extracted with ethyl acetate (10 mL) for three times. The combined organic layer was dried over anhydrous MgSO4 and filtered. After removal of the solvent in vacuo, the residue was purified by column chromatography (ethyl acetate/hexane) to afford the pure product.
2-[2-(3-bromophenyl)ethyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
99%
With calcium chloride In chloroform-d1 at 110℃; for 12h; Glovebox;
6 Calcium chloride catalyzes the reaction of 3-bromostyrene with pinacol borane, the process is as follows:
In the glove box, 3 mol% calcium chloride, 0.2 mmol of 3-bromostyrene, 0.4 mmol of pinacol borane, and 50 μl of CDCl3 were successively added to the reaction flask, and then removed from the glove box and stirred at 110° C. for 12 h to obtain 61.4 mg of product in 99% yield by NMR.
89%
With fac-[Mn(1,2-bis(di-isopropylphosphino)ethane)(CO)3(CH2CH2CH3)] In tetrahydrofuran at 80℃; for 24h; Sealed tube; Inert atmosphere;
With bis(1,5-cyclooctadiene)diiridium(I) dichloride; 1,4-di(diphenylphosphino)-butane In tetrahydrofuran at 20℃; for 18h;
2,2'-(2-(3-bromophenyl)ethane-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
With zirconocene dichloride; lithium methanolate In toluene at 100℃; for 8h; Inert atmosphere;
43 Example 43 A method for preparing geminal diboron compounds by selective 1,1-diboration of olefins:
Add Cp2ZrCl2 (0.01 mmol, 2.9 mg) to the reaction tube in sequence,MeOLi (0.2 mmol, 7.6 mg), toluene (1 mL), pinacol borane 2a (0.6 mmol, 87 μL), 3-bromostyrene 1p (0.2 mmol, 26 μL),The reaction was stirred at 100 °C for 8 h under a nitrogen (1 atm) atmosphere. GC-MS detection reaction is completed.Add 3 mL of methanol at room temperature, then spin-dry the solvent under reduced pressure,Purify the product by silica gel column chromatography, using petroleum ether: ethyl acetate (10 mL: 1 mL) as eluent,1,1-[bis(pinacol borate)]-3-bromobenzeneethane was obtained as light yellow oil3p (70 mg, 80%).
80%
With zirconocene dichloride; lithium methanolate In toluene at 100℃; Inert atmosphere;
2,2,2-trichloroethyl 2-(3-bromophenyl)aziridine-1-carboxylate[ No CAS ]
2,2,2-trichloroethyl 2-(3-bromophenyl)aziridine-1-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
1: 88 % ee
2: 98%
With Co(3,5-di<SUP>t</SUP>Bu-QingPhyrin); potassium carbonate In chlorobenzene at 20℃; for 24h; Schlenk technique; Inert atmosphere; Sealed tube; enantioselective reaction;
V. General Procedure for Enantioselective Aziridination of Styrenes
General procedure: To an over-dried Schlenk tube, [Co(Por)] (2 mol %) and K2CO3 (0.5 mmol) were added.The Schlenk tube was then evacuated and backfilled with nitrogen for 3 times. TheTeflon screw cap was replaced with a rubber septum and TrocN3 (0.1 mmol), styrene(0.3 mmol) and PhCl (1 mL) were added. The Schlenk tube was then purged withnitrogen for 2 minutes and the rubber septum was replaced with a Teflon screw cap.The mixture was then stirred at room temperature for 24 h. After the reaction finished,the resulting mixture was concentrated in vacuo and the residue was purified by flashsilica gel chromatography to afford the desired products. The silica gel was pre-treatedwith 1% Et3N/hexanes. In most cases, the product was visualized on TLC using UVlamp and/or the cerium ammonium molybdate (CAM) stain.
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