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Product Details of [ 7228-38-8 ]

CAS No. :7228-38-8 MDL No. :MFCD00010842
Formula : C7H5ClO2 Boiling Point : -
Linear Structure Formula :- InChI Key :ODQPZHOXLYATLC-UHFFFAOYSA-N
M.W : 156.57 Pubchem ID :138966
Synonyms :

Safety of [ 7228-38-8 ]

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

Application In Synthesis of [ 7228-38-8 ]

* 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.

  • Downstream synthetic route of [ 7228-38-8 ]

[ 7228-38-8 ] Synthesis Path-Downstream   1~101

  • 1
  • [ 7228-38-8 ]
  • [ 32316-92-0 ]
  • [ 228715-55-7 ]
YieldReaction ConditionsOperation in experiment
96% With Pd(dba)2*o-C6H4-<P(cyclohex)2>-<C(Me)(-OCH2CH2O-)>; cesium fluoride In 1,4-dioxane at 100 - 110℃;
96% With cesium fluoride; bis(dibenzylideneacetone)-palladium(0); 2’-(dicyclohexylphosphino)acetophenone ethylene ketal In 1,4-dioxane at 100℃; for 7h;
  • 2
  • [ 75-77-4 ]
  • [ 7228-38-8 ]
  • 4,7-bis(trimethylsilyl)-5-chloro-1,3-benzodioxole [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% With lithium diisopropyl amide In tetrahydrofuran at -78 - 20℃;
  • 3
  • [ 7228-38-8 ]
  • [ 33513-42-7 ]
  • 5-chloro-1,3-benzodioxole-4-carboxaldehyde [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% Stage #1: 5-chloro-1,3-benzodioxole With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 0.25h; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran at -78 - 20℃;
  • 4
  • [ 7228-38-8 ]
  • [ 4791-89-3 ]
YieldReaction ConditionsOperation in experiment
90% With styrene; [2,2]bipyridinyl; sodium hydride In tetrahydrofuran for 3h; Heating;
  • 5
  • [ 75-77-4 ]
  • [ 7228-38-8 ]
  • [ 52287-50-0 ]
YieldReaction ConditionsOperation in experiment
Stage #1: 5-chloro-1,3-benzodioxole With ethidium Bromide; magnesium; iron(II) chloride In tetrahydrofuran at 22 - 52℃; for 23h; Stage #2: chloro-trimethyl-silane In tetrahydrofuran
  • 6
  • [ 7228-38-8 ]
  • [ 274-09-9 ]
YieldReaction ConditionsOperation in experiment
100% With 4-methyl-morpholine; tetrahydroxydiboron; 5%-palladium/activated carbon In 1,2-dichloro-ethane at 50℃; for 5h;
Stage #1: 5-chloro-1,3-benzodioxole With ethidium Bromide; magnesium; iron(II) chloride In tetrahydrofuran at 22 - 52℃; for 23h; Stage #2: With water In tetrahydrofuran
100 %Chromat. In isopropyl alcohol for 15h; Irradiation; Inert atmosphere;
  • 7
  • [ 7228-38-8 ]
  • [ 153704-11-1 ]
  • 3-(benzo[d][1,3]dioxol-5-yl)-1-methylindolin-2-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
56% With palladium diacetate; sodium t-butanolate; tricyclohexylphosphine In 1,4-dioxane at 70℃; for 12h;
56% With palladium diacetate; sodium t-butanolate; tricyclohexylphosphine In 1,4-dioxane at 70℃;
  • 8
  • [ 7228-38-8 ]
  • [ 541-16-2 ]
  • di-tert-butyl 2-(3,4-methylenedioxyphenyl)malonate [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With bis(η3-allyl-μ-chloropalladium(II)); sodium t-butanolate In 1,4-dioxane at 100℃; for 12h;
  • 9
  • [ 7228-38-8 ]
  • [ 105-56-6 ]
  • [ 83751-78-4 ]
YieldReaction ConditionsOperation in experiment
86% With monophosphine 1,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphino)ferrocene; bis(η3-allyl-μ-chloropalladium(II)); sodium phosphate In toluene at 100℃;
  • 10
  • [ 7228-38-8 ]
  • [ 105-53-3 ]
  • [ 77069-04-6 ]
YieldReaction ConditionsOperation in experiment
85% With potassium phosphate; monophosphine 1,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphino)ferrocene; bis(dibenzylideneacetone)-palladium(0) In toluene at 100℃;
76% With potassium phosphate; di-tert-butyl(neopentyl)phosphine; bis(dibenzylideneacetone)-palladium(0) In toluene at 100℃; for 24h; General Procedure for the Arylation of Diethyl Malonate with Aryl Bromides (Table 3). General procedure: Reactions were conducted using standard dry box techniques and all solvents were distilled oversodium. To a screw capped vial was added Pd(dba)2 (0.020 mmol), DTBNpP (0.040mmol), andK3PO4 (3.0 mmol). The vial was sealed with a septa screw cap and removed from the glove box.To the vial was added toluene (3.0 mL), aryl chloride (1.0 mmol), and diethyl malonate (1.2mmol). The reaction mixture was stirred at 100 °C for 24 hours and the conversion of the arylchloride was then measured by GC. The crude reaction mixture was filtered through a plug ofCelite and then concentrated in vacuo. The concentrate was then purified by columnchromatography on silica gel.
  • 11
  • [ 274-09-9 ]
  • [ 7228-38-8 ]
YieldReaction ConditionsOperation in experiment
96.2% With chlorine In chloroform at 35℃; for 2h; 1.1 Step 1: Preparation of 5-chlorobenzodioxole Example 1: In a reaction flask equipped with a stirrer, a reflux condenser, and a dropping funnel, 0.5000 g of benzodioxole, 10 ml of chloroform was added, and the mixture was stirred and dissolved in a dropping funnel, and 5 ml of chloroform was added. Slowly pass 1.005 g of chlorine gas, control the temperature of the reaction solution to 35 ° C, and add chlorine gas to the chloroform solution for about 5 minutes. After the completion of the addition, the reaction was stirred for 2 hours, then washed twice with water, and the organic layer was combined, washed with brine, dried over anhydrous sodium sulfate and evaporated. The yield is 96.2%.
93% With ammonium persulfate; N-chloro-succinimide; oxygen; methylene green In acetonitrile at 20℃; for 24h; Irradiation; regioselective reaction; 4.2. General procedure for the chlorination of arenes and heteroarenes General procedure: To an oven-dried flask was added a magnetic stir bar, methylene green (9.1 mg, 0.05 equiv, 0.025 mmol), ammonium peroxodisulfate (11.4 mg, 0.1 equiv, 0.05 mmol), arene/heteroarene (1 equiv, 0.5 mmol), acetonitrile (2.5 mL), and then N-chlorosuccinimide (73.4 mg, 1.1 equiv, 0.55 mmol). The reaction mixture was stirred open to air at room temperature (20 C) in a white LED chamber for 24 h. For substrates that produced a mixture of mono- and dibrominated products upon full conversion, 2.2 equivalents (1.1 mmol) of N-chlorosuccinimide was employed. Upon completion of the reaction, the crude mixture was evaporated under pressure and the chlorinated product was isolated via column chromatography on silica gel.
92% With N-chloro-succinimide In various solvent(s) at 27℃; for 1h;
80% With ammonium cerium(IV) nitrate; acetyl chloride In acetonitrile at 20℃; for 8h;
75% With trichloroisocyanuric acid; brilliant green carbocation In acetonitrile at 20℃; for 0.25h; Irradiation; regioselective reaction;
72.6% With 1,3-dichloro-5,5-dimethylhydantoin In acetic acid at 60 - 90℃; for 1h;
59.7% With sulfuryl dichloride In Methylenedioxybenzene at 30 - 35℃; for 4h;
85.6 %Chromat. With 1,3-dichloro-5,5-dimethylhydantoin In acetic acid at 60 - 90℃; for 1h;
With aluminum (III) chloride; sulfuryl dichloride; diphenyl sulfide for 1.7h; 2.b Sulphuryl chloride (72.5 ml) was added dropwise during 1.7 hours to a stirred mixture of benzodioxole (100 g), aluminium trichloride (0.43 g) and diphenyl sulphide (0.55 ml). Once the reaction started with the evolution of sulphur dioxide, the reaction mixture was cooled in a water bath to a temperature of approximately 22°C. After completion of the addition, the reaction mixture was stirred at ambient temperature for 45 minutes. The reaction mixture was degassed under vacuum and filtered and the filtrate was distilled at atmospheric pressure using a Vigreux distillation column. There was thus obtained 5-chloro- 1, 3-benzodioxole; b. p. 185-187°C ; NMR Spectrum: (CDC13) 6.0 (s, 2H); 6.7 (d, 1H); 6.75- 6.9 (m, 2H).
With sulfuryl dichloride; diphenyl sulfide at 20 - 22℃; for 0.75h; 2; 23 Sulphuryl chloride (72.5 ml) was added dropwise during 1.7 hours to a stirred mixture of benzodioxole (100 g), aluminium trichloride (0.43 g) and diphenyl sulphide (0.55 ml). Once the reaction started with the evolution of sulphur dioxide, the reaction mixture was cooled in a water bath to a temperature of approximately [22C.] After completion of the addition, the reaction mixture was stirred at ambient temperature for 45 minutes. The reaction mixture was degassed under vacuum and filtered and the filtrate was distilled at atmospheric pressure using a Vigreux distillation column. There was thus obtained 5-chloro- 1,3-benzodioxole ; b. p. [185-187C] ; NMR Spectrum : (CDC13) 6.0 (s, 2H); 6.7 (d, 1H); 6.75-6. 9 (m, 2H).

  • 12
  • [ 7228-38-8 ]
  • [ 124-38-9 ]
  • [ 379229-83-1 ]
YieldReaction ConditionsOperation in experiment
84% Stage #1: 5-chloro-1,3-benzodioxole With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 0.5h; Stage #2: carbon dioxide In tetrahydrofuran at -78 - 20℃;
Stage #1: 5-chloro-1,3-benzodioxole With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78℃; for 0.75h; Stage #2: carbon dioxide In tetrahydrofuran; hexane at 20℃; for 1.5h; 2.b A mixture of diisopropylamine (4.92 ml) and THF (100 ml) was cooled to-78°C and n-butyllithium (2.5 M in hexane, 14 ml) was added dropwise. The mixture was stirred at - 78°C for 15 minutes. 5-Chloro-1, 3-benzodioxole (3.73 ml) was added dropwise and the reaction mixture was stirred at-78°C for 30 minutes. Dry carbon dioxide gas was bubbled into the reaction mixture for 30 minutes. The resultant reaction mixture was allowed to warm to ambient temperature and was stirred for a further hour. Water was added and the organic solvent was evaporated. The residue was acidified to pH2 by the addition of 2N aqueous hydrochloric acid solution. The resultant solid was isolated and washed in turn with water and diethyl ether. There was thus obtained 5-chloro-1, 3-benzodioxole-4-carboxylic acid (5.4 g); NMR Spectrum: (DMSOd6) 6.15 (s, 2H), 7.0 (m, 2H), 13.7 (br s, 1H).
Stage #1: With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78℃; for 0.25h; Stage #2: 5-chloro-1,3-benzodioxole In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #3: carbon dioxide With hydrogenchloride more than 3 stages; 2; 23 A mixture of diisopropylamine (4.92 ml) and THF (100 ml) was cooled to-78C and n-butyllithium (2.5 M in hexane, 14 [ML)] was added dropwise. The mixture was stirred at [- 78C] for 15 minutes. [5-CHLORO-1,] 3-benzodioxole (3.73 ml) was added dropwise and the reaction mixture was stirred at-78C for 30 minutes. Dry carbon dioxide gas was bubbled into the reaction mixture for 30 minutes. The resultant reaction mixture was allowed to warm to ambient temperature and was stirred for a further hour. Water was added and the organic solvent was evaporated. The residue was acidified to pH2 by the addition [OF 2N] aqueous hydrochloric acid solution. The resultant solid was isolated and washed in turn with water and diethyl ether. There was thus obtained 5-chloro-1, 3-benzodioxole-4-carboxylic acid (5.4 g); NMR Spectrum : [(DMSOD6)] 6.15 (s, 2H), 7.0 (m, 2H), 13.7 (br s, 1H).
  • 13
  • [ 7228-38-8 ]
  • [ 153495-48-8 ]
  • E-[4-(benzo[1,3]dioxol-5-yl)but-3-enyloxy]triisopropylsilane [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% Stage #1: but-3-ynyloxy-triisopropyl-silane In tetrahydrofuran for 1h; Stage #2: 5-chloro-1,3-benzodioxole With n-butyllithium; triphenylphosphine In tetrahydrofuran; hexane at 200℃; for 0.666667h; microwave irradiation;
75% Stage #1: but-3-ynyloxy-triisopropyl-silane With Schwartz's reagent In tetrahydrofuran for 1h; Stage #2: 5-chloro-1,3-benzodioxole With n-butyllithium; triphenylphosphine In tetrahydrofuran; hexane at 200℃; for 0.666667h;
75% Stage #1: but-3-ynyloxy-triisopropyl-silane With Schwartz's reagent In tetrahydrofuran for 1h; Stage #2: 5-chloro-1,3-benzodioxole With n-butyllithium; triphenylphosphine In tetrahydrofuran; hexane at 200℃; for 0.666667h; microwave irradiation; Further stages.;
  • 14
  • [ 7228-38-8 ]
  • [ 2633-57-0 ]
  • [ 24382-05-6 ]
YieldReaction ConditionsOperation in experiment
97% Stage #1: triallyl(phenyl)silane With tetrabutyl ammonium fluoride In tetrahydrofuran; water at 20℃; for 1h; Stage #2: 5-chloro-1,3-benzodioxole With XPhos In tetrahydrofuran; water at 80℃; for 14h;
  • 15
  • [ 7228-38-8 ]
  • [ 647842-35-1 ]
  • [ 89346-90-7 ]
YieldReaction ConditionsOperation in experiment
94% Stage #1: triallyl(4-methoxylphenyl)silane With tetrabutyl ammonium fluoride In tetrahydrofuran; water at 20℃; for 1h; Stage #2: 5-chloro-1,3-benzodioxole With XPhos In tetrahydrofuran; water at 80℃; for 4h;
  • 16
  • [ 7228-38-8 ]
  • [ 960-16-7 ]
  • [ 24382-05-6 ]
YieldReaction ConditionsOperation in experiment
90% With tris(dibenzylideneacetone)dipalladium (0); 2,8,9-tribenzyl-2,3,8,9-tetraaza-1-phosphabicyclo[3,3,3]undecane; cesium fluoride In 1,4-dioxane at 110℃; for 45h;
  • 17
  • [ 7228-38-8 ]
  • [ 119-93-7 ]
  • N-[4-(4-benzo[d][1,3]dioxol-5-ylamino-3-methylphenyl)-2-methylphenyl]benzo[d][1,3]dioxol-5-amine [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With sodium t-butanolate In 1,4-dioxane at 100℃;
  • 18
  • [ 7228-38-8 ]
  • [ 693-02-7 ]
  • 4-(1-hexyn-1-yl)-1,2-(methylenedioxy)benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
52% With triethylamine In 2,2,2-trifluoroethanol for 30h; Irradiation;
  • 19
  • C17H20N2O [ No CAS ]
  • [ 7228-38-8 ]
  • 5-[1-(4-methoxyphenyl)prop-1-enyl]benzo[d][1,3]dioxole [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With lithium tert-butoxide; XPhos In 1,4-dioxane at 90℃; for 16h;
  • 20
  • [ 7228-38-8 ]
  • [ 379229-84-2 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: LDA / tetrahydrofuran / 0.5 h / -78 °C 1.2: 84 percent / tetrahydrofuran / -78 - 20 °C 2.1: 81 percent / diphenoxyphosphoryl azide; Et3N / dioxane / 4 h / 100 °C
  • 21
  • [ 274-09-9 ]
  • [ 7228-38-8 ]
  • [ 6120-31-6 ]
YieldReaction ConditionsOperation in experiment
With N-chloro-succinimide; chloro-trimethyl-silane; In acetonitrile; at 20℃; for 1h; General procedure: To a solution of 4-bromoanisole (200.8 mg, 1.09 mmol, 1.0 equiv) in acetonitrile (2 mL) was added N-chlorosuccinimide(NCS) (158.3 mg, 1.19 mmol, 1.1 equiv) at rt to give a slightly cloudy mixture. Chlorotrimethylsilane (TMSCl) (14 muL, 0.11 mmol, 0.1 equiv) was then added drop-wise to the reaction mixture. Within a few minutes, the reaction mixture became clear pale yellow solution. The mixture continued to stir at rt for 1 h and was diluted with hexane. The biphasic mixture was concentrated on a rotary evaporator to a crude white solid-oil mixture. This mixture was taken up in hexane and filtered through a short plug of SiO2 and eluted with 5-10% EtOAc-hexane solution. The clear filtrate was concentrated to obtain a mixture of 4-bromo-2-chloro-1-methoxybenzene (2a-Cl) and 2,4-dichloro-1-methoxybenzene (2a-diCl) 237.0 mg (88% of 2a-Cl and 11% of 2a-diCl,based on NMR ratio 2a-Cl: 2a-diCl = 7.1: 1.0; as a pale yellow solid).
  • 22
  • [ 7228-38-8 ]
  • [ 95-93-2 ]
  • [ 274-09-9 ]
  • [ 954367-93-2 ]
YieldReaction ConditionsOperation in experiment
76% With triethylamine In 2,2,2-trifluoroethanol for 7h; Photolysis;
  • 23
  • [ 110-91-8 ]
  • [ 7228-38-8 ]
  • [ 1021359-42-1 ]
YieldReaction ConditionsOperation in experiment
86% With sodium t-butanolate In toluene at 80℃; for 16h;
71% With C50H61Cl2N3Pd; potassium <i>tert</i>-butylate In 1,4-dioxane at 100℃; for 2h;
  • 24
  • [ 7228-38-8 ]
  • [ 1012060-59-1 ]
YieldReaction ConditionsOperation in experiment
90.6% With N-iodo-succinimide; trifluoroacetic acid In acetonitrile at 20℃; for 24h; 2.a Step 2a. 5-Chloro-6-iodobenzo[d][1,3]dioxole (Compound 0107) A solution of compound 0106 (2.0 g, 12.77 mmol), acetonitrile (80 mL), TFA (2.9 g) and NIS (8.6 g, 38.3 mmol) was stirred at room temperature for 24 h. The solvent was removed under high vacuum and the crude product was purified by column chromatography on silica gel (petroleum) to yield the title compound 0107 as a white solid (3.27 g, 90.6%): 1H NMR (DMSO-d6) δ 6.10 (s, 2H), 7.25 (s, 1H), 7.45 (s, 1H).
50% With N-iodo-succinimide; trifluoroacetic acid In acetonitrile at 20℃; for 24h; Inert atmosphere; Darkness;
  • 25
  • [ 7228-38-8 ]
  • [ 3612-20-2 ]
  • [ 443143-01-9 ]
YieldReaction ConditionsOperation in experiment
97% Stage #1: 1-phenylmethyl-4-piperidone With tris-(dibenzylideneacetone)dipalladium(0); toluene-4-sulfonic acid hydrazide; lithium tert-butoxide; XPhos In 1,4-dioxane for 0.0166667h; Inert atmosphere; Stage #2: 5-chloro-1,3-benzodioxole In 1,4-dioxane at 110℃; for 12h; Inert atmosphere;
  • 26
  • [ 7228-38-8 ]
  • [ 118486-94-5 ]
  • 5-furan-2-ylbenzo<1,3>dioxole [ No CAS ]
YieldReaction ConditionsOperation in experiment
95% With Pd(OAc)2/XPhos; cesium fluoride In 1,2-dimethoxyethane at 80℃; for 4h; Inert atmosphere;
  • 27
  • [ 7228-38-8 ]
  • [ 68971-87-9 ]
  • 2-methyl-3',4'-methylenedioxy-1,1'-biphenyl [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% With palladium diacetate; cesium fluoride; XPhos In 1,2-dimethoxyethane at 80℃; for 4h; Inert atmosphere;
  • 28
  • [ 7228-38-8 ]
  • potassium ferrocyanide [ No CAS ]
  • [ 4421-09-4 ]
YieldReaction ConditionsOperation in experiment
58% With palladium(II) trifluoroacetate; 2-(di-tert-butylphosphino)-1-(2,6-diisopropylphenyl)-1H-imidazole; sodium carbonate In N,N-dimethyl acetamide at 140℃; for 16h; Inert atmosphere;
  • 29
  • [ 7228-38-8 ]
  • [ 2620-44-2 ]
YieldReaction ConditionsOperation in experiment
99% With tris-(dibenzylideneacetone)dipalladium(0); t-BuBrettPhos; tris(3,5-dioxaheptyl)amine; sodium nitrite In <i>tert</i>-butyl alcohol at 130℃; for 24h; regioselective reaction;
  • 30
  • [ 7228-38-8 ]
  • [ 14268-66-7 ]
YieldReaction ConditionsOperation in experiment
86% With ammonium sulfate; bis(1,5-cyclooctadiene)nickel (0); sodium t-butanolate at 100 - 110℃; for 12h;
82% With ammonium hydroxide; potassium phosphate; copper(l) iodide; N1,N2-bis(5-methyl-[1,1'-biphenyl]-2-yl)oxalamide In water; dimethyl sulfoxide at 110℃; for 24h; Inert atmosphere;
64% With bis[chloro(1,2,3-trihapto-allylbenzene)palladium(II)]; N-[2-(di(1-adamantyl)phosphino)phenyl]morpholine; ammonia; sodium t-butanolate In 1,4-dioxane at 110℃; for 18h; Inert atmosphere; chemoselective reaction;
  • 31
  • [ 104-53-0 ]
  • [ 7228-38-8 ]
  • [ 126266-78-2 ]
YieldReaction ConditionsOperation in experiment
59% With pyrrolidine; 2-(di-tert-butylphosphino)-1-(2-methoxyphenyl)-1H-pyrrole; bis(dibenzylideneacetone)-palladium(0) In N,N-dimethyl acetamide at 140℃; for 4h; Inert atmosphere; Molecular sieve;
  • 32
  • [ 7228-38-8 ]
  • [ 1254223-87-4 ]
  • [ 1254223-89-6 ]
YieldReaction ConditionsOperation in experiment
98% Stage #1: (S)-N'-(2-methoxycyclohexylidene)-4-methylbenzenesulfonohydrazide With tris-(dibenzylideneacetone)dipalladium(0); lithium tert-butoxide; XPhos In 1,4-dioxane for 0.0166667h; Inert atmosphere; Stage #2: 5-chloro-1,3-benzodioxole In 1,4-dioxane at 110℃; for 4h; Inert atmosphere; optical yield given as %ee; regioselective reaction;
  • 33
  • [ 7228-38-8 ]
  • [ 182482-25-3 ]
  • [ 1251914-01-8 ]
  • 34
  • [ 7228-38-8 ]
  • [ 3195-78-6 ]
  • [ 1256647-42-3 ]
  • 35
  • [ 7228-38-8 ]
  • 2-(2-hydroxyprop-2-yl)cyclohexyl(dimethyl)phenylsilane [ No CAS ]
  • [ 24382-05-6 ]
  • C11H22OSi [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 73% 2: > 95 %Chromat. With 1,1'-bis-(diphenylphosphino)ferrocene; (1,2-dimethoxyethane)dichloronickel(II); caesium carbonate; zinc; tricyclohexylphosphine In 1,2-dimethoxyethane; N,N-dimethyl-formamide at 20 - 60℃; for 30h; Inert atmosphere; chemoselective reaction;
  • 36
  • [ 7228-38-8 ]
  • potassiumhexacyanoferrate(II) trihydrate [ No CAS ]
  • [ 4421-09-4 ]
YieldReaction ConditionsOperation in experiment
90% With 2-[2-(dicyclohexylphosphino)-phenyl]-1-methyl-1H-indole; palladium diacetate; sodium carbonate; triethylamine In water; acetonitrile at 70℃; for 18h;
71% With di-tert-butyl{2′-isopropoxy-[1,1′-binaphthalen]-2-yl}phosphane; palladium diacetate; potassium carbonate; phenylboronic acid In water; <i>tert</i>-butyl alcohol at 100℃; for 6h; Inert atmosphere; Schlenk technique; general procedures for the cyanation of aryl chlorides and mesylates General procedure: An oven-dried Schlenk tube was evacuated and backfilled with nitrogen. The Schlenk tube was charged with Pd(OAc)2 (4.5 mg, 0.02 mmol ), L1 (36.5 mg, 0.08 mmol), PhB(OH)2 (6.1 mg, 0.05 mmol), and t-BuOH (2 mL), and the mixture was stirred for half hour at 50 °C. After cooling to r.t., aryl chloride or mesylates (1.00 mmol), K4[Fe(CN)6]·3H2O (211.2 mg, 0.50 mmol), K2CO3 (138.2 mg, 1.00 mmol), and H2O (2 mL) were added. The septum was replaced with an inside reflux condenser, and then the Schlenk tube was placed in an oil bath preheated to 100 °C (120 °C for aryl mesylates) with stirring for 6 h (24 h for aryl mesylates). Then the reaction mixture was allowed to cool to r.t., extracted with CH2Cl2, and concentrated under reduced pressure. The crude material was purified by column chromatography on silica gel.
  • 37
  • [ 7228-38-8 ]
  • [ 67-64-1 ]
  • [ 4676-39-5 ]
YieldReaction ConditionsOperation in experiment
94% With potassium phosphate; 2-(2,6-dimethoxyphenyl)-1-methyl-3-(diphenylphosphino)-1H-indole; palladium diacetate at 90℃; for 18h; Inert atmosphere; Schlenk technique;
72% With bis[chloro(1,2,3-trihapto-allylbenzene)palladium(II)]; N-[2-(di(1-adamantyl)phosphino)phenyl]morpholine; caesium carbonate at 90℃; for 16h; Inert atmosphere; sealed vial;
71% With (R)-1-[(SP)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-tert-butylphosphine; [Pd(π-cinnamyl)Cl]2; caesium carbonate at 25℃; for 48h; Sealed tube; Inert atmosphere; Glovebox;
37% With bis(1,5-cyclooctadiene)nickel (0); (R)-1-[(Sp)-2-(dicyclohexylphosphanyl)ferrocenylethyl]diphenylphosphane; cesium fluoride at 120℃; for 18h; Inert atmosphere;
97 %Chromat. With potassium phosphate; 3,6-di-tert-butyl-9-(2-(dicyclohexylphosphanyl)phenyl)-9H-carbazole; bis(dibenzylideneacetone)-palladium(0) at 90℃; for 18h; Inert atmosphere; Schlenk technique; Sealed tube; Molecular sieve;

  • 38
  • [ 7228-38-8 ]
  • [ 1071-36-9 ]
  • [ 1304676-18-3 ]
  • 39
  • [ 7228-38-8 ]
  • 3-methyl-1,3-diphenylcyclobutanol [ No CAS ]
  • [ 1359763-71-5 ]
YieldReaction ConditionsOperation in experiment
95% With 1,4-bis(dicyclohexylphosphino)butane di-trifluoroborate; palladium diacetate; sodium t-butanolate In toluene at 110℃; for 14h; Inert atmosphere;
  • 40
  • [ 7228-38-8 ]
  • [ 533-31-3 ]
YieldReaction ConditionsOperation in experiment
88% With copper acetylacetonate; N<SUP>1</SUP>-(4-hydroxy-2,6-dimethylphenyl)-N<SUP>2</SUP>-(4-hydroxy-3,5-dimethylphenyl)oxalamide; water In water; dimethyl sulfoxide at 130℃; for 24h; Schlenk technique; Inert atmosphere;
51% With trans-di(μ-acetato)bis[o-(di-o-tolyl-phosphino)benzyl]dipalladium(II); C29H45Pt; caesium carbonate In water; N,N-dimethyl-formamide at 130℃; for 0.5h; Inert atmosphere; Microwave irradiation;
  • 41
  • [ 7228-38-8 ]
  • [ 864832-30-4 ]
  • [ 1393651-46-1 ]
YieldReaction ConditionsOperation in experiment
63% Stage #1: 5-chloro-1,3-benzodioxole; (E)-N,1-bis(4-methoxyphenyl)ethan-1-imine With neopentylmagnesium bromide; 1,3-bis(mesityl)imidazolium chloride; cobalt(II) bromide In tetrahydrofuran at 0 - 20℃; Stage #2: With hydrogenchloride; water In tetrahydrofuran at 20℃; for 1h;
  • 42
  • [ 7228-38-8 ]
  • [ 98-86-2 ]
  • [ 40804-81-7 ]
YieldReaction ConditionsOperation in experiment
86% With bis[chloro(1,2,3-trihapto-allylbenzene)palladium(II)]; sodium t-butanolate In 1,4-dioxane at 90℃; for 18h; Inert atmosphere; Sealed tube;
84% With [Pd(IHept)(acac)Cl]; sodium t-butanolate In toluene at 100℃; for 16h; Glovebox;
  • 43
  • [ 7228-38-8 ]
  • [ 540-88-5 ]
  • [ 187141-67-9 ]
YieldReaction ConditionsOperation in experiment
88% With C41H55NPPd(1+)*CH3O3S(1-); lithium hexamethyldisilazane In toluene at 20℃; for 0.5h;
  • 44
  • [ 55077-52-6 ]
  • [ 7228-38-8 ]
  • methyl 4-(3,4-(methylenedioxy)benzyl)-4H-furo[3,2-b]indole-2-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
42% Stage #1: 4<i>H</i>-furo[3,2-<i>b</i>]indole-2-carboxylic acid methyl ester With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.0833333h; Stage #2: 5-chloro-1,3-benzodioxole In N,N-dimethyl-formamide at 20℃; for 0.333333h; 4.2.1. General procedure for synthesizing 4-substituted methyl 4H-furo[3,2-b]indole-2-carboxylate (5a-o, 9a-c) General procedure: A mixture of 4H-furo[3,2-b]indole-2-carboxylate (1 equiv) and NaH (3 equiv, 60%) in anhydrous DMF (5 mL) was stirred for 5 minat room temperature. A substituted-benzyl halide or heteroarylmethyl halide (4 equiv) was then added dropwise. The mixture was stirred at room temperature for 20 min. To this mixture was added 50 mL of ice cold water, and the solution was extracted with EtOAc. The organic phase was separately dried over anhydrous MgSO4, filtered, and evaporated under vacuum. The residue was purified by column chromatography on silica gel eluted with EtOAc:n-hexane (1:3, v/v) and then recrystallized from n-hexane/ EtOAc to obtain the pure compound (5a-o, 9a-c).
  • 45
  • [ 7228-38-8 ]
  • [ 1719-19-3 ]
  • [ 957768-42-2 ]
YieldReaction ConditionsOperation in experiment
98% With {(Pd{Fe(η5-C5H5)(η5-C5H3C(CH3)=NC6H4CH3-4)}(μ-Cl))2}; potassium carbonate; XPhos In acetonitrile at 110℃; for 16h; Inert atmosphere;
  • 46
  • [ 7228-38-8 ]
  • [ 111-86-4 ]
  • [ 1039864-69-1 ]
YieldReaction ConditionsOperation in experiment
88% With bis(1,5-cyclooctadiene)nickel (0); sodium t-butanolate In toluene at 100℃; for 20h; Inert atmosphere; Sealed tube;
73% With (2,2′-bis(biphenylphosphino)-1,1′-binaphthalene)Ni(η2-NC-Ph); sodium t-butanolate In toluene at 50℃; for 24h; Inert atmosphere; Glovebox;
  • 47
  • [ 7228-38-8 ]
  • C4H12BO4(1+)*K(1+) [ No CAS ]
  • [ 7228-35-5 ]
YieldReaction ConditionsOperation in experiment
76% With tris-(dibenzylideneacetone)dipalladium(0); tert-butyl XPhos In N,N-dimethyl-formamide at 100℃; Inert atmosphere;
  • 48
  • [ 7228-38-8 ]
  • [ 395-01-7 ]
  • [ 1577232-84-8 ]
YieldReaction ConditionsOperation in experiment
89% With potassium phosphate monohydrate; C28H41ClNPPd In toluene at 110℃; for 30h; Sealed tube;
  • 49
  • [ 7228-38-8 ]
  • [ 22092-92-8 ]
  • 3,4-methylendioxyphenyl-N,N-diisopropylaminoborane [ No CAS ]
YieldReaction ConditionsOperation in experiment
With palladium diacetate; triethylamine; potassium iodide; XPhos In ethyl acetate at 50℃; for 16h; Inert atmosphere; Schlenk technique;
With palladium diacetate; triethylamine; potassium iodide; XPhos at 50℃; Inert atmosphere; 106 Example 106: Preparation of 5-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-l,3- benzodioxole In a reaction flask charged with Pd(OAc)2 (4.5 mg, 0.02 mmol), potassium iodide (83 mg, 0.5 mmol), and XPhos (28 mg, 0.06 mmol) under argon atmosphere was added, in this following order: anhydrous solvent (2 mL), Et3N (0.4 mL, 3 mmol), 5- chlorobenzo[20 (2 mL), and the mixture was stirred for 4 h at room temperature. The reaction mixture was diluted with Et20 (10 mL), and the organic phase was washed first with a solution of HC1 (0.1 N, 2x10 mL), followed by an aqueous solution of CuCl2 (50g/L, 3x10 mL), dried over anhydrous Na2S04, filtered and concentrated under vacuum. The crude oil was passed through a pad of silica gel, eluting with Et20. The resulting filtrate was concentrated under vacuum to afford 5- (4,4,5,5- tetramethyl-l,3,2-dioxaborolan-2-yl)-l,3-benzodioxole (218 mg, 88%). 1H NMR (300 MHz, CDCI3) δ 7.35 (dd, IH, J 7.7, 1.1 Hz), 7.24 (d, IH, J 0.8 Hz), 6.83 (d, IH, J 7.7 Hz), 5.95 (s, 2H), 1.32 (s, 12H); 13C NMR (100 MHz, CDC13) δ 163.48, 161.84, 130.42, 129.59, 121.04, 118.38, 84.24, 25.0; nB NMR (96 MHz, CDC13) δ +30.63; MS (EI) tR = 9.594 min; m/z: 248 (M+, 100%).
With palladium diacetate; triethylamine; potassium iodide; XPhos at 50℃; Inert atmosphere; 106 Preparation of 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-benzodioxole In a reaction flask charged with Pd(OAc)2 (4.5 mg, 0.02 mmol), potassium iodide (83 mg, 0.5 mmol), and XPhos (28 mg, 0.06 mmol) under argon atmosphere was added, in this following order: anhydrous solvent (2 mL), Et3N (0.4 mL, 3 mmol), 5-chlorobenzo[d][1,3]dioxole (0.12 mL, 1 mmol) and diisopropylaminoborane (0.3 mL, 2 mmol). The reaction was then heated at 50 °C. After total consumption of either starting material, the reaction was cooled at -5 °C, quenched with anhydrous MeOH (2 mL) and stirred for 1 h at room temperature. All volatiles were removed under vacuum before adding pinacol (153 mg, 1.3 mmol) in Et2O (2 mL), and the mixture was stirred for 4 h at room temperature. The reaction mixture was diluted with Et2O (10 mL), and the organic phase was washed first with a solution ofHCl (0.1 N, 2x10 mL), followed by an aqueous solution of CuCl2 (50g/L, 3x10 mL), dried over anhydrous Na2SO4 filtered and concentrated under vacuum. The crude oil was passed through a pad of silica gel, eluting with Et2O. The resulting filtrate was concentrated under vacuum to afford 5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-benzodioxole (218 mg, 88%).
  • 51
  • [ 16620-96-5 ]
  • [ 7228-38-8 ]
  • [ 20071-04-9 ]
YieldReaction ConditionsOperation in experiment
41% Stage #1: 2-methyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline With boron trifluoride diethyl etherate In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Stage #2: With sec.-butyllithium In tetrahydrofuran; pentane at -78℃; for 0.5h; Stage #3: 5-chloro-1,3-benzodioxole With sec.-butyllithium In tetrahydrofuran at -78℃; for 0.75h; 6,7-Dimethoxy-2-methyl-1-(3,4-methylenedioxyphenyl)-1,2,3,4-tetrahydroisoquinoline [(±)-Cryptostyline I, 2f]11 General procedure: Into a flame-dried two-necked round-bottomed flask, equipped witha magnetic stirrer bar, septum cap and a bubbler, was taken a solutionof N-methyl-1,2,3,4-tetrahydroisoquinoline (3; 200 mg, 1.36mmol, 1 equiv) or the substituted analogue 9 (1.36 mmol, 1 equiv)in anhydrous THF (10 mL) under an inert N2 atmosphere. It wascooled to 0 °C and BF3·OEt2 (0.25 mL, 1.63 mmol, 1.2 equiv) wasadded dropwise. The turbid white solution was stirred at 0 °C for 30min. It was then cooled to -78 °C and s-BuLi [1.43 mL (2.6 M inpentane), 2.99 mmol, 2.2 equiv] was added dropwise. A deep redcolor (indicative of benzylic carbanion formation) appeared imme-diately. The solution was stirred at the same temperature for 30 min.The second instalment of s-BuLi [1.96 mL (2.6 M in pentane), 4.08mmol, 3 equiv] was added followed by the addition of a solution ofaryl halide 7 (4.08 mmol, 3 equiv) in THF (1-2 mL). The reactionmixture was stirred at -78 °C for 45 min and was allowed to warmto r.t. slowly over a period of 4-5 h. The reaction was quenched withaq 10% HCl (15 mL) and the contents were poured into Et2O (25mL). The aqueous layer was separated and the organic layer wasfurther extracted with aq 10% HCl (2 × 15 mL). The combinedaqueous layers were washed with Et2O (2 × 20 mL) to remove nonbasicimpurities, made alkaline with solid Na2CO3, and extractedwith CHCl3 (4 × 15 mL). The combined organic layers were washedwith brine (20 mL) and dried (Na2SO4). The solvent was evaporatedin vacuo to afford the crude product, which was purified by flashcolumn chromatography using 230-400 mesh silica gel. Elutionwith EtOAc-hexane (3:7) or MeOH-CHCl3 (2:98) afforded the 1-aryl substituted product. Further elution of the column with samesolvent afforded the unreacted starting material (Tables 2 and 3); 6,7-Dimethoxy-2-methyl-1-(3,4-methylenedioxyphenyl)-1,2,3,4-tetrahydroisoquinoline [(±)-Cryptostyline I, 2f]11Yield: 129 mg (41%); yellow solid; mp 116-117 °C (Lit.11 mp 117-118 °C).1H NMR (400 MHz, CDCl3): δ = 6.65 (dd, J = 7.9, 1.4 Hz, 1 H,ArH), 6.62 (d, J = 7.8 Hz, 1 H, ArH), 6.61 (d, J = 1.2 Hz, 1 H, ArH),6.46 (s, 1 H, ArH), 6.04 (s, 1 H, ArH), 5.84 (d, J = 1.1 Hz, 1 H,OCH2O), 5.83 (d, J = 1.2 Hz, 1 H, OCH2O), 3.98 (s, 1 H, C1-H),3.75 (s, 3 H, OCH3), 3.53 (s, 3 H, OCH3), 3.09-3.02 (m, 1 H, C3-H),3.00-2.95 (m, 1 H, C3-H), 2.58 (dd, J = 15.7, 3.0 Hz, 1 H, C4-H),2.45 (td, J = 10.8, 3.5 Hz, 1 H, C4-H), 2.14 (s, 3 H, NCH3).
  • 52
  • [ 7228-38-8 ]
  • [ 494-55-3 ]
  • [ 1620820-67-8 ]
YieldReaction ConditionsOperation in experiment
32% Stage #1: N-methyl-6,7-methylenedioxy-1,2,3,4-tetrahydroisoquinoline With boron trifluoride diethyl etherate In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Stage #2: With sec.-butyllithium In tetrahydrofuran; pentane at -78℃; for 0.5h; Stage #3: 5-chloro-1,3-benzodioxole With sec.-butyllithium In tetrahydrofuran at -78℃; for 0.75h; 2-Methyl-6,7-methylenedioxy-1-(3,4-methylenedioxyphenyl)-1,2,3,4- tetrahydroisoquinoline (2l) General procedure: Into a flame-dried two-necked round-bottomed flask, equipped witha magnetic stirrer bar, septum cap and a bubbler, was taken a solutionof N-methyl-1,2,3,4-tetrahydroisoquinoline (3; 200 mg, 1.36mmol, 1 equiv) or the substituted analogue 9 (1.36 mmol, 1 equiv)in anhydrous THF (10 mL) under an inert N2 atmosphere. It wascooled to 0 °C and BF3·OEt2 (0.25 mL, 1.63 mmol, 1.2 equiv) wasadded dropwise. The turbid white solution was stirred at 0 °C for 30min. It was then cooled to -78 °C and s-BuLi [1.43 mL (2.6 M inpentane), 2.99 mmol, 2.2 equiv] was added dropwise. A deep redcolor (indicative of benzylic carbanion formation) appeared imme-diately. The solution was stirred at the same temperature for 30 min.The second instalment of s-BuLi [1.96 mL (2.6 M in pentane), 4.08mmol, 3 equiv] was added followed by the addition of a solution ofaryl halide 7 (4.08 mmol, 3 equiv) in THF (1-2 mL). The reactionmixture was stirred at -78 °C for 45 min and was allowed to warmto r.t. slowly over a period of 4-5 h. The reaction was quenched withaq 10% HCl (15 mL) and the contents were poured into Et2O (25mL). The aqueous layer was separated and the organic layer wasfurther extracted with aq 10% HCl (2 × 15 mL). The combinedaqueous layers were washed with Et2O (2 × 20 mL) to remove nonbasicimpurities, made alkaline with solid Na2CO3, and extractedwith CHCl3 (4 × 15 mL). The combined organic layers were washedwith brine (20 mL) and dried (Na2SO4). The solvent was evaporatedin vacuo to afford the crude product, which was purified by flashcolumn chromatography using 230-400 mesh silica gel. Elutionwith EtOAc-hexane (3:7) or MeOH-CHCl3 (2:98) afforded the 1-aryl substituted product. Further elution of the column with samesolvent afforded the unreacted starting material (Tables 2 and 3); 2-Methyl-6,7-methylenedioxy-1-(3,4-methylenedioxyphenyl)-1,2,3,4- tetrahydroisoquinoline (2l)Yield: 102 mg (32%); yellow solid; mp 164-165 °C.IR (neat): 2981, 2896, 1478, 1236, 1039 cm-1.1H NMR (400 MHz, CDCl3): δ = 6.72 (dd, J = 7.9, 1.4 Hz, 1 H,ArH), 6.69 (d, J = 7.7 Hz, 1 H, ArH), 6.67 (d, J = 1.1 Hz, 1 H, ArH),6.51 (s, 1 H, ArH), 6.09 (s, 1 H, ArH), 5.92 (d, J = 1.5 Hz, 1 H,OCH2O), 5.90 (d, J = 1.5 Hz, 1 H, OCH2O), 5.81 (d, J = 1.4 Hz, 1H, OCH2O), 5.79 (d, J = 1.4 Hz, 1 H, OCH2O), 4.00 (s, 1 H, C1-H),3.16-3.08 (m, 1 H, C3-H), 3.05-3.01 (m, 1 H, C3-H), 2.62 (dt, J =15.8, 3.1 Hz, 1 H, C4-H), 2.50 (td, J = 11.0, 3.6 Hz, 1 H, C4-H), 2.19(s, 3 H, NCH3).13C NMR (75 MHz, CDCl3): δ = 147.9, 146.9, 145.9, 145.8, 138.0,131.6, 127.3, 122.8, 109.3, 108.3, 107.8, 107.5, 100.8, 100.5, 71.3,52.4, 44.3, 29.6.MS (APCI): m/z = 312.41 [M + H]+.Anal. Calcd for C18H17NO4: C, 69.44; H, 5.50; N, 4.50. Found: C,69.12; H, 5.62; N, 4.59.
  • 53
  • [ 7228-38-8 ]
  • [ 54893-23-1 ]
  • [ 1620820-71-4 ]
YieldReaction ConditionsOperation in experiment
40% Stage #1: 7-methoxy-N-methyl-1,2,3,4-tetrahydroisoquinoline With boron trifluoride diethyl etherate In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Stage #2: With sec.-butyllithium In tetrahydrofuran; pentane at -78℃; for 0.5h; Stage #3: 5-chloro-1,3-benzodioxole With sec.-butyllithium In tetrahydrofuran at -78℃; for 0.75h; 6-Methoxy-2-methyl-1-(3,4-methylenedioxyphenyl)-1,2,3,4-tetrahydroisoquinoline(2r) General procedure: Into a flame-dried two-necked round-bottomed flask, equipped witha magnetic stirrer bar, septum cap and a bubbler, was taken a solutionof N-methyl-1,2,3,4-tetrahydroisoquinoline (3; 200 mg, 1.36mmol, 1 equiv) or the substituted analogue 9 (1.36 mmol, 1 equiv)in anhydrous THF (10 mL) under an inert N2 atmosphere. It wascooled to 0 °C and BF3·OEt2 (0.25 mL, 1.63 mmol, 1.2 equiv) wasadded dropwise. The turbid white solution was stirred at 0 °C for 30min. It was then cooled to -78 °C and s-BuLi [1.43 mL (2.6 M inpentane), 2.99 mmol, 2.2 equiv] was added dropwise. A deep redcolor (indicative of benzylic carbanion formation) appeared imme-diately. The solution was stirred at the same temperature for 30 min.The second instalment of s-BuLi [1.96 mL (2.6 M in pentane), 4.08mmol, 3 equiv] was added followed by the addition of a solution ofaryl halide 7 (4.08 mmol, 3 equiv) in THF (1-2 mL). The reactionmixture was stirred at -78 °C for 45 min and was allowed to warmto r.t. slowly over a period of 4-5 h. The reaction was quenched withaq 10% HCl (15 mL) and the contents were poured into Et2O (25mL). The aqueous layer was separated and the organic layer wasfurther extracted with aq 10% HCl (2 × 15 mL). The combinedaqueous layers were washed with Et2O (2 × 20 mL) to remove nonbasicimpurities, made alkaline with solid Na2CO3, and extractedwith CHCl3 (4 × 15 mL). The combined organic layers were washedwith brine (20 mL) and dried (Na2SO4). The solvent was evaporatedin vacuo to afford the crude product, which was purified by flashcolumn chromatography using 230-400 mesh silica gel. Elutionwith EtOAc-hexane (3:7) or MeOH-CHCl3 (2:98) afforded the 1-aryl substituted product. Further elution of the column with samesolvent afforded the unreacted starting material (Tables 2 and 3); 6-Methoxy-2-methyl-1-(3,4-methylenedioxyphenyl)-1,2,3,4-tetrahydroisoquinoline(2r)Yield: 134 mg (40%); white solid; mp 110-113 °C.IR (neat): 2963, 2810, 1490, 1276, 1079 cm-1.1H NMR (400 MHz, CDCl3): δ = 6.65 (dd, J = 7.8, 1.4 Hz, 1 H,ArH), 6.61 (d, J = 7.8 Hz, 1 H, ArH), 6.60 (d, J = 1.4 Hz, 1 H, ArH),6.48 (d, J = 1.7 Hz, 1 H, ArH), 6.45-6.42 (m, 2 H, ArH), 5.82 (d,J = 1.4 Hz, 1 H, OCH2O), 5.81 (d, J = 1.4 Hz, 1 H, OCH2O), 3.96(s, 1 H, C1-H), 3.65 (s, 3 H, OCH3), 3.15-3.08 (m, 1 H, C3-H), 3.00-2.95 (m, 1 H, C3-H), 2.66-2.62 (m, 1 H, C4-H), 2.45 (td, J = 11.3,3.7 Hz, 1 H, C4-H), 2.12 (s, 3 H, NCH3).13C NMR (75 MHz, CDCl3): δ = 157.7, 147.9, 146.8, 138.3, 135.2,130.9, 129.5, 122.8, 112.5, 112.2, 109.3, 107.4, 100.7, 70.9, 54.8,52.5, 44.3, 29.9.MS (APCI): m/z = 298.53 [M + H]+.Anal. Calcd for C18H19NO3: C, 72.71; H, 6.44; N, 4.71. Found: C,72.59; H, 6.35; N, 4.65.
  • 54
  • [ 7228-38-8 ]
  • 6-ethoxy-7-methoxy-2-methyl-1,2,3,4-tetrahydro-isoquinoline [ No CAS ]
  • [ 1620820-77-0 ]
YieldReaction ConditionsOperation in experiment
39% Stage #1: 6-ethoxy-7-methoxy-2-methyl-1,2,3,4-tetrahydro-isoquinoline With boron trifluoride diethyl etherate In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Stage #2: With sec.-butyllithium In tetrahydrofuran; pentane at -78℃; for 0.5h; Stage #3: 5-chloro-1,3-benzodioxole With sec.-butyllithium In tetrahydrofuran at -78℃; for 0.75h; 7-Ethoxy-6-methoxy-2-methyl-1-(3,4-methylenedioxyphenyl)-1,2,3,4-tetrahydroisoquinoline (2x) General procedure: Into a flame-dried two-necked round-bottomed flask, equipped witha magnetic stirrer bar, septum cap and a bubbler, was taken a solutionof N-methyl-1,2,3,4-tetrahydroisoquinoline (3; 200 mg, 1.36mmol, 1 equiv) or the substituted analogue 9 (1.36 mmol, 1 equiv)in anhydrous THF (10 mL) under an inert N2 atmosphere. It wascooled to 0 °C and BF3·OEt2 (0.25 mL, 1.63 mmol, 1.2 equiv) wasadded dropwise. The turbid white solution was stirred at 0 °C for 30min. It was then cooled to -78 °C and s-BuLi [1.43 mL (2.6 M inpentane), 2.99 mmol, 2.2 equiv] was added dropwise. A deep redcolor (indicative of benzylic carbanion formation) appeared imme-diately. The solution was stirred at the same temperature for 30 min.The second instalment of s-BuLi [1.96 mL (2.6 M in pentane), 4.08mmol, 3 equiv] was added followed by the addition of a solution ofaryl halide 7 (4.08 mmol, 3 equiv) in THF (1-2 mL). The reactionmixture was stirred at -78 °C for 45 min and was allowed to warmto r.t. slowly over a period of 4-5 h. The reaction was quenched withaq 10% HCl (15 mL) and the contents were poured into Et2O (25mL). The aqueous layer was separated and the organic layer wasfurther extracted with aq 10% HCl (2 × 15 mL). The combinedaqueous layers were washed with Et2O (2 × 20 mL) to remove nonbasicimpurities, made alkaline with solid Na2CO3, and extractedwith CHCl3 (4 × 15 mL). The combined organic layers were washedwith brine (20 mL) and dried (Na2SO4). The solvent was evaporatedin vacuo to afford the crude product, which was purified by flashcolumn chromatography using 230-400 mesh silica gel. Elutionwith EtOAc-hexane (3:7) or MeOH-CHCl3 (2:98) afforded the 1-aryl substituted product. Further elution of the column with samesolvent afforded the unreacted starting material (Tables 2 and 3); 7-Ethoxy-6-methoxy-2-methyl-1-(3,4-methylenedioxyphenyl)-1,2,3,4-tetrahydroisoquinoline (2x)Yield: 120 mg (39%); white solid; mp 88-90 °C.IR (neat): 2974, 2899, 1477, 1236, 1039 cm-1.1H NMR (400 MHz, CDCl3): δ = 6.64 (dd, J = 7.9, 1.4 Hz, 1 H,ArH), 6.61 (d, J = 7.7 Hz, 1 H, ArH), 6.60 (d, J = 1.0 Hz, 1 H, ArH),6.44 (s, 1 H, ArH), 6.02 (s, 1 H, ArH), 5.84 (d, J = 1.3 Hz, 1 H,OCH2O), 5.83 (d, J = 1.4 Hz, 1 H, OCH2O), 3.95 (s, 1 H, C1-H),3.73 (s, 3 H, OCH3), 3.72-3.65 (m, 2 H, OCH2CH3), 3.07-3.01 (m,1 H, C3-H), 2.99-2.94 (m, 1 H, C3-H), 2.56 (dd, J = 15.7, 3.1 Hz, 1H, C4-H), 2.44 (td, J = 10.8, 3.5 Hz, 1 H, C4-H), 2.13 (s, 3 H, NCH3),1.21 (t, J = 7 Hz, 3 H, OCH2CH3).13C NMR (75 MHz, CDCl3): δ = 147.9, 147.8, 146.8, 146.5, 138.0,130.4, 126.4, 122.7, 113.3, 111.1, 109.3, 107.3, 100.7, 70.8, 64.2,55.6, 52.3, 44.3, 29.0, 14.7.MS (APCI): m/z = 342.39 [M + H]+.Anal. Calcd for C20H23NO4: C, 70.36; H, 6.79; N, 4.10. Found: C,70.59; H, 6.52; N, 4.29.
  • 55
  • [ 1612-65-3 ]
  • [ 7228-38-8 ]
  • [ 1620820-62-3 ]
YieldReaction ConditionsOperation in experiment
40% Stage #1: 2-methyl-1,2,3,4-tetrahydroisoquinoline With boron trifluoride diethyl etherate In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Stage #2: With sec.-butyllithium In tetrahydrofuran; pentane at -78℃; for 0.5h; Stage #3: 5-chloro-1,3-benzodioxole With sec.-butyllithium In tetrahydrofuran at -78℃; for 0.75h; 2-Methyl-1-(3,4-methylenedioxyphenyl)-1,2,3,4-tetrahydroisoquinoline(1f) General procedure: Into a flame-dried two-necked round-bottomed flask, equipped witha magnetic stirrer bar, septum cap and a bubbler, was taken a solutionof N-methyl-1,2,3,4-tetrahydroisoquinoline (3; 200 mg, 1.36mmol, 1 equiv) or the substituted analogue 9 (1.36 mmol, 1 equiv)in anhydrous THF (10 mL) under an inert N2 atmosphere. It wascooled to 0 °C and BF3·OEt2 (0.25 mL, 1.63 mmol, 1.2 equiv) wasadded dropwise. The turbid white solution was stirred at 0 °C for 30min. It was then cooled to -78 °C and s-BuLi [1.43 mL (2.6 M inpentane), 2.99 mmol, 2.2 equiv] was added dropwise. A deep redcolor (indicative of benzylic carbanion formation) appeared imme-diately. The solution was stirred at the same temperature for 30 min.The second instalment of s-BuLi [1.96 mL (2.6 M in pentane), 4.08mmol, 3 equiv] was added followed by the addition of a solution ofaryl halide 7 (4.08 mmol, 3 equiv) in THF (1-2 mL). The reactionmixture was stirred at -78 °C for 45 min and was allowed to warmto r.t. slowly over a period of 4-5 h. The reaction was quenched withaq 10% HCl (15 mL) and the contents were poured into Et2O (25mL). The aqueous layer was separated and the organic layer wasfurther extracted with aq 10% HCl (2 × 15 mL). The combinedaqueous layers were washed with Et2O (2 × 20 mL) to remove nonbasicimpurities, made alkaline with solid Na2CO3, and extractedwith CHCl3 (4 × 15 mL). The combined organic layers were washedwith brine (20 mL) and dried (Na2SO4). The solvent was evaporatedin vacuo to afford the crude product, which was purified by flashcolumn chromatography using 230-400 mesh silica gel. Elutionwith EtOAc-hexane (3:7) or MeOH-CHCl3 (2:98) afforded the 1-aryl substituted product. Further elution of the column with samesolvent afforded the unreacted starting material (Tables 2 and 3); 2-Methyl-1-(3,4-methylenedioxyphenyl)-1,2,3,4-tetrahydroisoquinoline(1f)Yield: 145 mg (40%); colorless oil.IR (neat): 2904, 2843, 1550, 1235, 1082 cm-1.1H NMR (400 MHz, CDCl3): δ = 6.98-6.93 (m, 2 H, ArH), 6.88-6.84 (m, 1 H, ArH), 6.66 (dd, J = 7.8, 1.4 Hz, 1 H, ArH), 6.63-6.61(m, 2 H, ArH), 6.55 (d, J = 7.8 Hz, 1 H, ArH), 5.83 (d, J = 1.4 Hz,1 H, OCH2O), 5.81 (d, J = 1.4 Hz, 1 H, OCH2O), 4.01 (s, 1 H, C1-H), 3.18-3.10 (m, 1 H, C3-H), 3.02-2.97 (m, 1 H, C3-H), 2.65 (dt,J = 15.8, 2.8 Hz, 1 H, C4-H), 2.47 (td, J = 11.3, 3.7 Hz, 1 H, C4-H),2.13 (s, 3 H, NCH3).13C NMR (75 MHz, CDCl3): δ = 147.9, 146.9, 138.1, 138.1, 134.0,128.0, 127.9, 126.0, 125.9, 122.9, 109.8, 107.4, 100.7, 71.3, 52.5,44.4, 29.8.MS (APCI): m/z = 268.44 [M + H]+.HRMS (ESI): m/z [M + H]+ calcd for C17H18NO2: 268.1332; found:268.1331.
  • 56
  • [ 7228-38-8 ]
  • [ 1667-01-2 ]
  • 2-(benzo[d][1,3]dioxol-5-yl)-1-mesitylethanp-1-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With [Pd(IHept)(acac)Cl]; sodium t-butanolate In toluene at 100℃; for 16h; Glovebox;
  • 57
  • [ 7228-38-8 ]
  • [ 585-32-0 ]
  • N-(2-phenylpropan-2-yl)benzo[d][1,3]dioxol-5-amine [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With C26H33N2P; C39H46N3O3PPdS; sodium t-butanolate In 1,4-dioxane at 80℃; for 6h; Inert atmosphere;
  • 58
  • [ 7228-38-8 ]
  • [ 363-72-4 ]
  • [ 1178578-00-1 ]
YieldReaction ConditionsOperation in experiment
80% With N-methyl-2-phenyl-3-(dicyclohexylphosphino)-1H-indole; palladium diacetate; sodium phosphate; Trimethylacetic acid In dichloromethane; N,N-dimethyl acetamide at 100℃; for 24h; Schlenk technique; Inert atmosphere;
  • 59
  • [ 7228-38-8 ]
  • [ 73183-34-3 ]
  • 2-(6-chlorobenzo[d][1,3]dioxol-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; cyclopentyl methyl ether; 1,1'-di(pyridin-2-yl)-1,1',3,3'-tetrahydro-2,2'-bibenzo[d][1,3,2]diazaborole at 50℃; for 16h; Schlenk technique; Inert atmosphere;
67% With bis(1,5-cyclooctadiene)diiridium(I) dichloride; 1-(4,4'-di-tert-butyl-[2,2'-bipyridin]-6-yl)-2-(dimethyl(phenyl)silyl)-2,3-dihydro-1H-benzo[d][1,3,2]diazaborole Inert atmosphere; Schlenk technique; Sealed tube; 4.4. General Procedure for Iridium-Catalyzed arene C-H borylation Using NNB-type Ligand General procedure: B2pin2, [IrCl(COD)]2 (1.0 mol%), preligand 1 (2.0 mol%), and (hetero)arene (0.2 mmol, ifsolid) were placed in a dried Schlenk flask (15 mL in volume) equipped with a stirring bar. Afterevacuating and refilling the flask with dry nitrogen three times, (hetero)arene (0.2 mmol, if liquid)and methoxycyclopentane (CAPE, 0.5 mL) were added with syringes under a stream of nitrogen.The resulting mixture was stirred at the corresponding temperature for the assigned time. After cooling to room temperature, the reaction mixture was concentrated and then purified by columnchromatography on silica gel to give the target product (The spectra data for the borylated compoundscan be seen in the Supplementary Material).
  • 60
  • [ 7228-38-8 ]
  • [ 73183-34-3 ]
  • 2,2'-(5-chlorobenzo[d][1,3]dioxole-4,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With bis(1,5-cyclooctadiene)diiridium(I) dichloride; 1-(4,4'-di-tert-butyl-[2,2'-bipyridin]-6-yl)-2-(dimethyl(phenyl)silyl)-2,3-dihydro-1H-benzo[d][1,3,2]diazaborole Inert atmosphere; Schlenk technique; Sealed tube; 4.4. General Procedure for Iridium-Catalyzed arene C-H borylation Using NNB-type Ligand General procedure: B2pin2, [IrCl(COD)]2 (1.0 mol%), preligand 1 (2.0 mol%), and (hetero)arene (0.2 mmol, ifsolid) were placed in a dried Schlenk flask (15 mL in volume) equipped with a stirring bar. Afterevacuating and refilling the flask with dry nitrogen three times, (hetero)arene (0.2 mmol, if liquid)and methoxycyclopentane (CAPE, 0.5 mL) were added with syringes under a stream of nitrogen.The resulting mixture was stirred at the corresponding temperature for the assigned time. After cooling to room temperature, the reaction mixture was concentrated and then purified by columnchromatography on silica gel to give the target product (The spectra data for the borylated compoundscan be seen in the Supplementary Material).
65% With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; cyclopentyl methyl ether; 1,1'-di(pyridin-2-yl)-1,1',3,3'-tetrahydro-2,2'-bibenzo[d][1,3,2]diazaborole at 100℃; for 16h; Schlenk technique; Inert atmosphere;
  • 61
  • [ 7228-38-8 ]
  • [ 7699-79-8 ]
  • C27H21NO2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% With bis(1,5-cyclooctadiene)nickel (0); potassium hexamethylsilazane; 1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene In toluene at 45℃; for 16h;
  • 62
  • [ 7228-38-8 ]
  • [ 74199-03-4 ]
YieldReaction ConditionsOperation in experiment
61% Stage #1: 5-chloro-1,3-benzodioxole With lithium 4,4′-di-tert-butylbiphenylide In tetrahydrofuran; diethyl ether; decane at -95℃; for 0.0833333h; Inert atmosphere; Schlenk technique; Stage #2: With zinc(II) chloride In tetrahydrofuran; diethyl ether; decane at -95 - 20℃; Inert atmosphere; Schlenk technique; LiDBB-Mediated Preparation of Aryllithium and Zinc Reagent from Aryl Chloride; General Procedure 1 (GP1) General procedure: Arylchloride (1 mmol, 1 equiv), decane (internal standard, 0.2 mL), and anhydrous Et2O (5 mL) were sequentially added to a pre-dried Schlenk flask equipped with a magnetic stirrer and a rubber septum under argon. The flask was cooled to -95°C (methanol/liquid nitrogen bath) followed by the dropwise addition of a previously prepared LiDBB solution (ca. 0.25 M in THF, 2 mmol, 8 mL, 2 equiv). After addition and stirring for 5 min at this temperature, aryllithium reagent 2 was obtained. The corresponding arylzinc reagent 5 was prepared by the addition of ZnCl2 solution (1.0 M in THF, 1 mmol, 1 mL) followed by warming to r.t. The yield of the aryllithium or arylzinc reagent was determined by GC analysis of an aliquot of the resulting arylzinc reagent quenched with asolution of iodine in anhydrous THF in the presence of an internal standard (decane).
  • 63
  • [ 7228-38-8 ]
  • [ 98-92-0 ]
  • N-(benzo[d][1,3]dioxol-5-yl)nicotinamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% With potassium phosphate; [(π-allyl)Pd(tBuBrettPhos)]OTf In <i>tert</i>-butyl alcohol at 110℃; for 1.5h; Schlenk technique; Inert atmosphere; Sealed tube;
  • 64
  • [ 7228-38-8 ]
  • [ 90-41-5 ]
  • N-([1,1'-biphenyl]-2-yl)benzo[d][1,3]dioxol-5-amine [ No CAS ]
YieldReaction ConditionsOperation in experiment
94% With dicyclohexyl-(2′,4′,6′-triisopropyl-3,6-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine; [(π-crotyl)Pd(BrettPhos)]OTf; sodium t-butanolate In tetrahydrofuran at 80℃; for 0.166667h; Schlenk technique; Inert atmosphere;
  • 65
  • [ 7228-38-8 ]
  • [ 34583-80-7 ]
  • 3-methyl-1-[3,4-(methylenedioxy)phenyl]-2,3,4,5-tetrahydro-1H-3-benzazepine [ No CAS ]
YieldReaction ConditionsOperation in experiment
27% Stage #1: 3-methyl-2,3,4,5-tetrahydro-1H-3-benzazepine With sec.-butyllithium In tetrahydrofuran; pentane at -78℃; for 1h; Inert atmosphere; Stage #2: 5-chloro-1,3-benzodioxole With sec.-butyllithium In tetrahydrofuran; pentane at -78 - 20℃; regioselective reaction; 1-Aryl-3-methyl-2,3,4,5-tetrahydro-1H-3-benzazepines 1a-l, 10a-f; General Procedure for the Lithiation/Arylation Reaction General procedure: To a flame-dried, 2-necked, round-bottomed flask, equipped with a magnetic stirrer bar, septum cap, and a bubbler, was added a solution of the appropriate 3-methyl-2,3,4,5-tetrahydro-1H-3-benzazepine 7(1.55 mmol, 1 equiv) in anhyd THF (8 mL) under an inert N2 atmosphere.The soln was cooled to -78 °C and 2.7 M s-BuLi in pentane(1.3 mL, 3.4 mmol, 2.2 equiv) was added. A deep red color, which was indicative of benzylic carbanion formation, appeared immediately.The solution was stirred at this temperature for 1 h. The second instalment of 2.7 M s-BuLi in pentane (1.7 mL, 4.65 mmol, 3 equiv) wasadded followed by the addition of a solution of aryl halide 9 (4.65mmol, 3 equiv) in THF (1 mL). The mixture was stirred at -78 °C for 45 min and then it was allowed to warm to r.t. slowly over a period of 4-5 h. The reaction was quenched with 10% HCl (10 mL) and the contents were poured into Et2O (25 mL). The aqueous layer was separated and the organic layer was further extracted with 10% HCl (3 × 10 mL).The combined aqueous layers were washed with Et2O (2 × 10 mL) to remove non-basic impurities, made alkaline with solid Na2CO3 and extracted with CHCl3 (4 × 10 mL). The organic layer was washed with brine and dried (anhyd Na2SO4). The solvent was evaporated in vacuo to afford the crude basic product, which was purified by flash chromatography (silica gel, EtOAc-hexane, 8:2) to furnish the 1-aryl-substituted product. Further elution of the column with same solvent afforded the unreacted starting material. The first Et2O layer (25 mL) and the second Et2O washings (2 × 10 mL) were combined, washedwith brine, and dried (anhyd Na2SO4). The solvent was evaporated tofurnish the crude non-basic material.
  • 66
  • [ 7228-38-8 ]
  • [ 78495-54-2 ]
  • 7,8-dimethoxy-3-methyl-1-[3,4-(methylenedioxy)phenyl]-2,3,4,5-tetrahydro-1H-3-benzazepine [ No CAS ]
YieldReaction ConditionsOperation in experiment
29% Stage #1: 7,8-dimethoxy-3-methyl-2,3,4,5-tetrahydro-1H-3-benzazepine With sec.-butyllithium In tetrahydrofuran; pentane at -78℃; for 1h; Inert atmosphere; Stage #2: 5-chloro-1,3-benzodioxole With sec.-butyllithium In tetrahydrofuran; pentane at -78 - 20℃; regioselective reaction; 1-Aryl-3-methyl-2,3,4,5-tetrahydro-1H-3-benzazepines 1a-l, 10a-f; General Procedure for the Lithiation/Arylation Reaction General procedure: To a flame-dried, 2-necked, round-bottomed flask, equipped with a magnetic stirrer bar, septum cap, and a bubbler, was added a solution of the appropriate 3-methyl-2,3,4,5-tetrahydro-1H-3-benzazepine 7(1.55 mmol, 1 equiv) in anhyd THF (8 mL) under an inert N2 atmosphere.The soln was cooled to -78 °C and 2.7 M s-BuLi in pentane(1.3 mL, 3.4 mmol, 2.2 equiv) was added. A deep red color, which was indicative of benzylic carbanion formation, appeared immediately.The solution was stirred at this temperature for 1 h. The second instalment of 2.7 M s-BuLi in pentane (1.7 mL, 4.65 mmol, 3 equiv) wasadded followed by the addition of a solution of aryl halide 9 (4.65mmol, 3 equiv) in THF (1 mL). The mixture was stirred at -78 °C for 45 min and then it was allowed to warm to r.t. slowly over a period of 4-5 h. The reaction was quenched with 10% HCl (10 mL) and the contents were poured into Et2O (25 mL). The aqueous layer was separated and the organic layer was further extracted with 10% HCl (3 × 10 mL).The combined aqueous layers were washed with Et2O (2 × 10 mL) to remove non-basic impurities, made alkaline with solid Na2CO3 and extracted with CHCl3 (4 × 10 mL). The organic layer was washed with brine and dried (anhyd Na2SO4). The solvent was evaporated in vacuo to afford the crude basic product, which was purified by flash chromatography (silica gel, EtOAc-hexane, 8:2) to furnish the 1-aryl-substituted product. Further elution of the column with same solvent afforded the unreacted starting material. The first Et2O layer (25 mL) and the second Et2O washings (2 × 10 mL) were combined, washedwith brine, and dried (anhyd Na2SO4). The solvent was evaporated tofurnish the crude non-basic material.
  • 67
  • [ 7228-38-8 ]
  • [ 33140-75-9 ]
  • 3-methyl-7,8-(methylenedioxy)-1-[3,4-(methylenedioxy)phenyl]-2,3,4,5-tetrahydro-1H-3-benzazepine [ No CAS ]
YieldReaction ConditionsOperation in experiment
25% Stage #1: 3-methyl-7,8-methylenedioxy-2,3,4,5-tetrahydro-1H-3-benzazepine With sec.-butyllithium In tetrahydrofuran; pentane at -78℃; for 1h; Inert atmosphere; Stage #2: 5-chloro-1,3-benzodioxole With sec.-butyllithium In tetrahydrofuran; pentane at -78 - 20℃; regioselective reaction; 1-Aryl-3-methyl-2,3,4,5-tetrahydro-1H-3-benzazepines 1a-l, 10a-f; General Procedure for the Lithiation/Arylation Reaction General procedure: To a flame-dried, 2-necked, round-bottomed flask, equipped with a magnetic stirrer bar, septum cap, and a bubbler, was added a solution of the appropriate 3-methyl-2,3,4,5-tetrahydro-1H-3-benzazepine 7(1.55 mmol, 1 equiv) in anhyd THF (8 mL) under an inert N2 atmosphere.The soln was cooled to -78 °C and 2.7 M s-BuLi in pentane(1.3 mL, 3.4 mmol, 2.2 equiv) was added. A deep red color, which was indicative of benzylic carbanion formation, appeared immediately.The solution was stirred at this temperature for 1 h. The second instalment of 2.7 M s-BuLi in pentane (1.7 mL, 4.65 mmol, 3 equiv) wasadded followed by the addition of a solution of aryl halide 9 (4.65mmol, 3 equiv) in THF (1 mL). The mixture was stirred at -78 °C for 45 min and then it was allowed to warm to r.t. slowly over a period of 4-5 h. The reaction was quenched with 10% HCl (10 mL) and the contents were poured into Et2O (25 mL). The aqueous layer was separated and the organic layer was further extracted with 10% HCl (3 × 10 mL).The combined aqueous layers were washed with Et2O (2 × 10 mL) to remove non-basic impurities, made alkaline with solid Na2CO3 and extracted with CHCl3 (4 × 10 mL). The organic layer was washed with brine and dried (anhyd Na2SO4). The solvent was evaporated in vacuo to afford the crude basic product, which was purified by flash chromatography (silica gel, EtOAc-hexane, 8:2) to furnish the 1-aryl-substituted product. Further elution of the column with same solvent afforded the unreacted starting material. The first Et2O layer (25 mL) and the second Et2O washings (2 × 10 mL) were combined, washedwith brine, and dried (anhyd Na2SO4). The solvent was evaporated tofurnish the crude non-basic material.
  • 68
  • [ 7228-38-8 ]
  • [ 93-55-0 ]
  • 2-(benzo[d][1,3]dioxol-5-yl)-1-phenylpropan-1-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With [Ni(1,3-bis[2,6-bis(diphenylmethyl)-4-methylphenyl]imidazole-2-ylidene)(cin)Cl]; sodium t-butanolate In toluene at 80℃; for 16h;
67% With dichloro(1,5-cyclooctadiene)palladium(II); keYPhos; sodium t-butanolate In tetrahydrofuran at 20℃; for 16h; Inert atmosphere; Glovebox;
  • 69
  • [ 7228-38-8 ]
  • [ 100-06-1 ]
  • [ 1314025-23-4 ]
YieldReaction ConditionsOperation in experiment
78% With [Ni(1,3-bis[2,6-bis(diphenylmethyl)-4-methylphenyl]imidazole-2-ylidene)(cin)Cl]; sodium t-butanolate In toluene at 80℃; for 16h;
  • 70
  • [ 7228-38-8 ]
  • [ 121-97-1 ]
  • α-(1,3-benzodioxol-5-yl)-4'-methoxypropiophenone [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With di-tert-butyl(neopentyl)phosphine; palladium diacetate; sodium t-butanolate In toluene at 80℃; for 24h; Inert atmosphere; Sealed tube; Glovebox;
  • 71
  • [ 7228-38-8 ]
  • 6,7,8,9-tetrahydro-8-methylpyrido[1,2-a]indol-9-one [ No CAS ]
  • C20H17NO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With bis(1,5-cyclooctadiene)nickel (0); (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl; sodium t-butanolate In toluene at 70℃; for 48h; enantioselective reaction;
  • 72
  • [ 7228-38-8 ]
  • [ 33715-53-6 ]
  • 1-fluoro-[3',4'-(methylenedioxy)phenyl-4-yl]benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
99% With 3-(dicyclohexylphosphino)-2-(2-methoxyphenyl)-1-methyl-1-H-indole; tetrabutyl ammonium fluoride; palladium diacetate In water at 110℃; for 3h; Schlenk technique; Inert atmosphere; Sealed tube;
  • 73
  • [ 7228-38-8 ]
  • C24H39BO2 [ No CAS ]
  • (R,E)-5-(5-methyl-1-phenylundec-3-en-5-yl)benzo[d][1,3]dioxole [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With palladium diacetate; potassium hydroxide; ruphos In 1,4-dioxane; water at 60℃; for 14h; Inert atmosphere; Sealed tube; enantiospecific reaction;
  • 74
  • [ 7228-38-8 ]
  • [ 621-82-9 ]
  • [ 51003-88-4 ]
YieldReaction ConditionsOperation in experiment
88% Stage #1: Cinnamic acid With potassium <i>tert</i>-butylate In ethanol at 20℃; for 1h; Inert atmosphere; Sealed tube; Stage #2: 5-chloro-1,3-benzodioxole With palladium(II) acetylacetonate; 1,10-Phenanthroline; tris-(o-tolyl)phosphine; copper(I) bromide In 1-methyl-pyrrolidin-2-one; quinoline; ethanol at 170℃; for 16h; Inert atmosphere; Sealed tube;
  • 75
  • [ 7228-38-8 ]
  • C9H13O2S(1-)*Na(1+) [ No CAS ]
  • [ 89346-90-7 ]
YieldReaction ConditionsOperation in experiment
96% With η3-1-tert-butylindenyl palladium chloride dimer In toluene at 70℃; for 4h; Inert atmosphere; Glovebox; Sealed tube;
  • 76
  • [ 7228-38-8 ]
  • C12H13OS(1-)*Na(1+) [ No CAS ]
  • 1-(3,4-methylenedioxyphenyl)naphthalene [ No CAS ]
YieldReaction ConditionsOperation in experiment
95% With η3-1-tert-butylindenyl palladium chloride dimer In toluene at 70℃; for 4h; Inert atmosphere; Glovebox; Sealed tube;
  • 77
  • [ 7228-38-8 ]
  • C9H10F3OS(1-)*Na(1+) [ No CAS ]
  • [ 1099595-82-0 ]
YieldReaction ConditionsOperation in experiment
94% With η3-1-tert-butylindenyl palladium chloride dimer In toluene at 70℃; for 4h; Inert atmosphere; Glovebox; Sealed tube;
  • 78
  • [ 94839-07-3 ]
  • [ 7228-38-8 ]
YieldReaction ConditionsOperation in experiment
90% With N-chloro-succinimide In acetonitrile at 80℃; for 24h;
  • 79
  • [ 557-21-1 ]
  • [ 7228-38-8 ]
  • [ 4421-09-4 ]
YieldReaction ConditionsOperation in experiment
91% Stage #1: zinc(II) cyanide With aluminum oxide; Ni(xantphos)(o-tolyl)Cl for 1h; Schlenk technique; Inert atmosphere; Sealed tube; Stage #2: 5-chloro-1,3-benzodioxole In 1-methyl-pyrrolidin-2-one at 20℃; for 24h; Schlenk technique; Inert atmosphere;
  • 80
  • [ 7228-38-8 ]
  • [ 20277-69-4 ]
  • 5-(methylsulfonyl)benzo[d][1,3]dioxole [ No CAS ]
YieldReaction ConditionsOperation in experiment
72% With potassium phosphate; copper(l) iodide; (2S,4R)-4-hydroxy-N-(2-methylnaphthalen-1-yl)pyrrolidine-2-carboxamide In dimethyl sulfoxide at 120℃; Sealed tube; Inert atmosphere;
  • 81
  • [ 7228-38-8 ]
  • [ 23277-04-5 ]
  • 2-benzyl-4-bromo-1-(5-chlorobenzo[d][1,3]dioxol-2-yl)-1,2-dihydroisoquinoline [ No CAS ]
YieldReaction ConditionsOperation in experiment
72% With tert.-butylhydroperoxide; copper acetylacetonate In water at 20℃; for 0.166667h;
  • 82
  • [ 1122-58-3 ]
  • [ 7228-38-8 ]
  • [ 201230-82-2 ]
  • C15H15N2O3(1+)*Cl(1-) [ No CAS ]
YieldReaction ConditionsOperation in experiment
With bis(tri-t-butylphosphine)palladium(0); 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In toluene at 150℃; for 24h;
  • 83
  • [ 7228-38-8 ]
  • [ 2554-06-5 ]
  • [ 7315-32-4 ]
  • 84
  • [ 7228-38-8 ]
  • C11H13NO3 [ No CAS ]
  • [ 109596-92-1 ]
YieldReaction ConditionsOperation in experiment
96.9% Stage #1: 5-chloro-1,3-benzodioxole With iodine; magnesium In tetrahydrofuran at 30℃; for 0.5h; Inert atmosphere; Stage #2: With copper(I) bromide dimethylsulfide complex In tetrahydrofuran at 0 - 20℃; for 0.333333h; Inert atmosphere; Stage #3: C11H13NO3 In tetrahydrofuran for 0.333333h; 4.12 Step 4: Preparation of N-(2-(benzo[d][1,3]dioxol-5-yl)ethyl)-2,3-dimethoxybenzamide 0.1352 g of magnesium strips and 0.0500 g of iodine were sequentially added to a dry three-necked flask, protected with N2, and then 4 mL of dry tetrahydrofuran was added thereto, and a part of 5-chlorobenzodioxole was added dropwise. After the initiation was successful, the remaining 5-chlorobenzodioxole was slowly added dropwise, and a total of 0.8013 g of 5-chlorobenzodioxole was added. The reaction was carried out at 30 ° C for 0.5 h in preparation for the next reaction.Example 12: 0.04210 g of CuBr.SMe2, 4 mL of THF was added to a dry three-necked flask at room temperature and stirred under N2 protection. The reaction solution was lowered to 0 ° C, and the Grignard reagent prepared in the step 2 was added dropwise, about 2 min dropwise, and the reaction was stirred for 20 min. Then, a mixed solution of 0.5818 g of 1-aziridine-2,3-dimethoxyphenylethanone and 4 mL of tetrahydrofuran was added dropwise to the reaction solution, and the mixture was added dropwise for about 2 minutes. After the completion of the dropwise addition, the reaction was continued for 20 minutes, and the reaction was stopped. The reaction was quenched with saturated ammonium chloride, then extracted with dichloromethane, the organic layers were combined, washed with saturated saline water, drying over anhydrous sodium sulfate, distilling off dichloromethane and separating the product by column chromatography. The yield was 96.9%.
  • 85
  • [ 7228-38-8 ]
  • [ 1589-49-7 ]
  • 5-(3-methoxypropoxy)benzo[d][1,3]dioxole [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With C12H10N(1-)*CH3O3S(1-)*Pd(2+)*C39H57O2P; sodium t-butanolate In 1,4-dioxane at 60℃; for 18h; Sealed tube; Schlenk technique; Inert atmosphere;
  • 86
  • [ 7228-38-8 ]
  • [ 108-98-5 ]
  • [ 1420042-93-8 ]
YieldReaction ConditionsOperation in experiment
82% With trans-[4,5-bis(diphenylphosphino)-9,9-dimethylxanthene](2-methylphenyl)nickel(II) chloride; C4H9ClZn*LiCl In tetrahydrofuran; toluene at 110℃; for 1h; Schlenk technique; Inert atmosphere;
  • 87
  • [ 7228-38-8 ]
  • [ 591-31-1 ]
  • [ 851958-75-3 ]
YieldReaction ConditionsOperation in experiment
86% With 1,10-Phenanthroline; 3-chloroprop-1-ene; trifluoroacetic acid; cobalt(II) bromide; zinc In acetonitrile at 80℃; for 16h; Inert atmosphere; Sealed tube;
  • 88
  • [ 98-00-0 ]
  • [ 7228-38-8 ]
  • C12H10O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With N<SUP>1</SUP>,N<SUP>2</SUP>-bis(naphthalen-1-ylmethyl)oxalamide; potassium <i>tert</i>-butylate; copper diacetate In 1,4-dioxane at 100℃; for 24h; Schlenk technique; Inert atmosphere; Molecular sieve;
  • 89
  • [ 7228-38-8 ]
  • [ 65864-64-4 ]
  • 5-(difluoromethyl)benzo[d][1,3]dioxole [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% With dicyclohexyl-(2′,4′,6′-triisopropyl-3,6-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine; cesium fluoride; bis(dibenzylideneacetone)-palladium(0) In 1,4-dioxane at 100℃; for 16h; Glovebox; Sealed tube;
  • 90
  • [ 6111-99-5 ]
  • [ 7228-38-8 ]
  • [ 24235-29-8 ]
YieldReaction ConditionsOperation in experiment
50% With bis(η3-allyl-μ-chloropalladium(II)); diisopropylamine; XPhos In toluene at 100℃; for 3.25h;
  • 91
  • [ 6165-69-1 ]
  • [ 7228-38-8 ]
  • 5-(thiophen-3-yl)benzo[d][1,3]dioxole [ No CAS ]
YieldReaction ConditionsOperation in experiment
94% With potassium phosphate; C46H52Cl3N3O2Pd In tetrahydrofuran; water at 60℃; for 4h;
  • 92
  • [ 7228-38-8 ]
  • [ 159326-68-8 ]
  • C13H10N4O2 [ No CAS ]
  • 93
  • [ 7228-38-8 ]
  • [ 108-94-1 ]
  • [ 63765-11-7 ]
YieldReaction ConditionsOperation in experiment
42% With dichloro(1,5-cyclooctadiene)palladium(II); keYPhos; sodium t-butanolate In tetrahydrofuran at 60℃; for 16h; Inert atmosphere; Glovebox;
  • 94
  • [ 3153-36-4 ]
  • [ 7228-38-8 ]
  • [ 99557-75-2 ]
YieldReaction ConditionsOperation in experiment
62% With nickel(II) bromide dimethoxyethane; pyridine-2,6-bis(N-cyanocarboxamidine); lithium chloride; zinc In 1-methyl-pyrrolidin-2-one at 80℃; for 24h; Inert atmosphere;
  • 95
  • [ 7228-38-8 ]
  • [ 73183-34-3 ]
  • [ 762-72-1 ]
  • (3-(benzo[d][1,3]dioxol-5-yl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl)trimethylsilane [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With FG-2909; nickel(II) chloride ethylene glycol dimethyl ether complex; lithium methanolate In ethyl acetate at 50℃; for 35h; Inert atmosphere; Sealed tube; 5 Example 5 In a glove box filled with argon, add nickel(II) chloride ethylene glycol dimethyl ether (5.5mg, 0.025mmol), ligand L8 (0.025mmol), Lithium methoxide (29.0mg, 0.75mmol), pinacol diborate (190.5mg, 0.75mmol) were dissolved in 2mL of dry ethyl acetate solvent, and then the above olefin (57.1mg, 0.5mmol) and the above aryl halide were added Substitute (117.4mg, 0.75mmol), The reaction tube was sealed and taken out of the glove box, and reacted at 50°C for 35 hours. After the reaction, the reaction solvent was removed by concentration under reduced pressure. Column chromatography was separated and purified to obtain the target product (colorless oil, yield 78%).
78% With FG-2909; nickel(II) chloride ethylene glycol dimethyl ether complex; lithium methanolate In ethyl acetate at 50℃; Inert atmosphere; regioselective reaction; General procedure: Under N2 atmosphere, an oven-dried 10 mL reaction tube which equipped with amagnetic stir bar and sealed with a rubber stopper sequentially was added NiCl2·DME(5.5 mg, 0.025 mmol, 5 mol %), L8 (4.2 mg, 0.025 mmol, 5 mol%), LiOMe (28.5 mg,0.75 mmol, 1.5 equiv), bis(pinacolato)diboron (2, 190.5 mg, 0.75 mmol, 1.5 equiv).Then anhydrous EA (2 mL), alkene (1, 0.5 mmol, 1.0 equiv), chlorobenzene (3, 0.75mmol, 1.5 equiv) were added and the mixture was stirred. After 17-36 h of stirring at50 °C, an aliquot of 20 μL was removed and analyzed by GC. The reaction vial wasdiluted with 4 mL of ethyl acetate and the resulting solution was filtered through Celite.The crude material was concentrated in vacuo and separated on a silica gel columnaffording the desired product boronate.
  • 96
  • [ 7228-38-8 ]
  • [ 124-38-9 ]
  • [ 4421-09-4 ]
YieldReaction ConditionsOperation in experiment
78% With nickel(II) acetylacetonate; potassium fluoride; phenylsilane; ammonia; zinc; bis(2-diphenylphosphinoethyl)phenylphosphine In 1-methyl-pyrrolidin-2-one at 90 - 140℃; for 20h; Sealed tube;
  • 97
  • [ 7228-38-8 ]
  • [ 57-13-6 ]
  • [ 4421-09-4 ]
YieldReaction ConditionsOperation in experiment
96% With nickel(II) acetylacetonate; potassium fluoride; phenylsilane; zinc; bis(2-diphenylphosphinoethyl)phenylphosphine In 1-methyl-pyrrolidin-2-one at 90 - 140℃; for 20h;
  • 98
  • [ 7228-38-8 ]
  • [ 104-82-5 ]
  • 5-[(4-methylphenyl)methyl]-1,3-benzodioxole [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With Ni(IBiox-6)[P(OEt)3]Br2; magnesium In tetrahydrofuran at 50℃; for 1h; Schlenk technique; Glovebox;
  • 99
  • [ 7228-38-8 ]
  • [ 617-89-0 ]
  • N-(furan-2-ylmethyl)benzo[d][1,3]dioxol-5-amine [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% With copper(l) iodide; C14H16N2O; caesium carbonate In N,N-dimethyl-formamide at 130℃; for 24h; Inert atmosphere; Sealed tube;
  • 100
  • [ 7228-38-8 ]
  • [ 124-38-9 ]
  • [ 94-53-1 ]
YieldReaction ConditionsOperation in experiment
75% With manganese; 2,9-dibutyl-4,7-dimethyl-1,10-phenanthroline; tetraethylammonium iodide; lithium acetate; cobalt(II) bromide In N,N-dimethyl acetamide at 100℃; for 12h; Inert atmosphere; Schlenk technique;
  • 101
  • [ 7228-38-8 ]
  • [ 78-59-1 ]
  • 3-(benzo[d][1,3]dioxol-5-ylmethyl)-5,5-dimethylcyclohex-2-enon [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% With 2-(2,6-dimethoxyphenyl)-1-methyl-3-(diphenylphosphino)-1H-indole; palladium diacetate; lithium tert-butoxide In 1,4-dioxane at 100℃; for 1h; Schlenk technique; Inert atmosphere;
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