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Transition-Metal-Free Borylation of Aryl Bromide Using a Simple Diboron Source
Lim, Taeho ; Ryoo, Jeong Yup ; Han, Min Su JOC,2020,85(16):10966-10972. DOI: 10.1021/acs.joc.0c01065 PubMed ID: 32806093
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Abstract: In this study, we developed a simple transition-metal-free borylation reaction of aryl bromides. Bis-boronic acid (BBA), was used, and the borylation reaction was performed using a simple procedure at a mild temperature. Under mild conditions, aryl bromides were converted to arylboronic acids directly without any deprotection steps and purified by conversion to trifluoroborate salts. The functional group tolerance was considerably high. The mechanism study suggested that this borylation reaction proceeds via a radical pathway.
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CAS No. : | 6793-92-6 | MDL No. : | MFCD00028016 |
Formula : | C13H11BrO | Boiling Point : | - |
Linear Structure Formula : | C6H5CH2OC6H4Br | InChI Key : | OUQSGILAXUXMGI-UHFFFAOYSA-N |
M.W : | 263.13 | Pubchem ID : | 138835 |
Synonyms : |
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Chemical Name : | 1-Bromo-4-(phenylmethoxy)benzene |
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: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Step 1 ; 3-(4-Benzyloxy-benzoyl)-azetidine-1-carboxylic aoid tert-butyl esterTo a stirred solution of 1-(Benzyloxy)-4-bromobenzene (32.3 g, 0.12 mol) in dry THF (250 mL) was added n-Butyl lithium (83 mL. 0.13 mol. 1.6 M solution in hexane) in drops at -78 C under nitrogen and the reaction mixture was stirred at same temperature for 1 nr. To this reaction mixture, a solution of fert-butyl 3- [methoxy(methyl)amlno]carbonyl}azetidine-1-carboxylate (25 g, 0.10 mol) in dry THF (150 mL) was added in drops. The reaction mixture was stirred at -78 C for 1 nr. After completion of reaction, the reaction mixture was quenched with ice water and extracted with ethyl acetate (2 x 200 mL). The combined organic layer washed with water (200 mL), brine (100 mL) and dried over sodium sulphate. The solvent was concentrated under reduced pressure; the crude product was slurred with pet ether (100 mL) and ethyl acetate (50 mL). The solids were filtered to afford (30g, 75 %) of the titled compound as white solid. TLC-Pet ether/ Ethyl acetate (8:2), R, = 0.7; 'H NMR (400MHz, DMSO-de) δ 7.84-7.82 (t. J = 8.0 Hz, 2H). 7.46-7.31 (m, 5H), 7.14-7.10 (m, 2H), 5.20 (s, 2H), 4.35-4.28 (m, 1H), 4.10 (s, 2H), 3.93 (s, 2H). 1.36 (s, 9H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With copper(l) iodide; potassium carbonate; N,N`-dimethylethylenediamine; In toluene; at 110℃; for 20h;Inert atmosphere; | To the round-bottom flask 1 - (benzyloxy) - 4-bromobenzene (2.00g, 7 . 60mmol), <strong>[109-11-5]morpholine-3-one</strong> (1.15g, 11 . 37mmol), cuprous iodide (290 mg, 1 . 52mmol), N, N '-dimethyl-ethylenediamine (0.4 ml, 4 . 00mmol), potassium carbonate (2.11g, 15 . 3mmol) and toluene (20 ml)is added, under nitrogen and heated to 110 C stirring 20 hours. Cooling to room temperature, add saturated ammonium chloride solution (20 ml) quenching the reaction, ethyl acetate (50 ml × 3) extraction. Combined with the phase, saturated salt water (50 ml) to wash, dry anhydrous sodium sulfate. Filtering, distilling off the solvent under reduced pressure, the crude product purification column chromatography (petroleum ether/ethyl acetate (v/v)=1/2), get white solid (1.81g, 84.0%). |
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