- 1
[ 583-55-1 ]
[ 4269-17-4 ]
| Yield | Reaction Conditions | Operation in experiment |
| 46% |
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.25 h; Inert atmosphere
Stage #2: at -78℃; Inert atmosphere
Stage #3: With n-butyllithium In tetrahydrofuran; hexane at -78 - 25℃; for 12.00 h; Inert atmosphere |
General procedure: A solution of butyllithium (1 equiv, 1.6 M in hexanes) or tert-butyllithium (2 equiv, 1.7 M in pentanes) was added dropwise to a solution of aryllithium precursor (1 equiv) in dry THF (2.5 mL/mmol) under argon at -78 °C. The mixture was stirred at -78 °C for 15 min and was then warmed up to the desired temperature. Either a rt solution of aryne precursor (1 or 1.2 equiv) in dry THF (2.5 mL/mmol) or the neat aryne precursor was added dropwise. If required, butyllithium (0.2 equiv) was added dropwise to the reaction medium. The mixture was stirred for 15 h from the desired temperature to 25 °C, quenched with water and extracted with Et2O. The combined organic layers were dried with Na2SO4 and concentrated under reduced pressure. The crude product was puried by column chromatography on silica gel, eluting with hexane/EtOAc or pentane/EtOAc mixtures. Compound 23e was prepared following the general procedure from 22b (246 mg, 1.1 mmol) and 2d (406 mg, 1.1 mmol, 1 equiv) using BuLi as the base and adding a -78 °C solution of 2d in THF onto the reaction medium at -78 °C, followed by 0.2 equiv of BuLi. 23e was obtained as a mixture of two atropo-diastereoisomers with a diastereoisomeric ratio of 66:34. The crude residue was purified by column chromatography (eluent: hexane/AcOEt 8/2) to give 23e as a pale yellow oil (84.5 mg, 0.165 mmol, 15percent) and 24d as a yellow solid byproduct (23.2 mg, 0.0770 mmol, 7percent). |
Reference：
[1] Tetrahedron, 2016, vol. 72, # 34, p. 5208 - 5220
[2] European Journal of Organic Chemistry, 2016, vol. 2016, # 4, p. 725 - 732
- 2
[ 54245-41-9 ]- [ 4269-17-4 ]
| Yield | Reaction Conditions | Operation in experiment |
| 80% |
for 12.00 h; Reflux |
To a 500 mL reaction flask, 50 mL of benzonitrile was added successively,70.7 g (0.3 mol) of o-dibromobenzene,68.4 g (0.45 mol) of cesium fluoride,Catalyst purged with argon was added bis (dibenzylideneacetone) palladium 0.86g (15mmol),Thiophene-2-carboxylate 2.86 g (15 mmol)And 7.0 g (15 mmol) of 1,1'-bis (di-t-butylphosphine) ferrocene,150 reaction 24h,filter,The filtrate was distilled to remove benzonitrile to give crude 2-bromo-2'-carbonitrile biphenyl.A 500 mL reaction flask was charged with crude 2-bromo-2'-carbonitrile biphenyl,Glacial acetic acid 80mL,Concentrated sulfuric acid 80mL.After heating and refluxing for 12 h,Cooled to room temperature,filter,To give a dark yellow solid,100 mL of water,100 mL of methanol,Recrystallization from 200 mL of cumene afforded 61.9 g of 4-bromofluorenone as a yellow solid in 80percent yield. |
Reference：
[1] Patent: CN105237379, 2016, A. Location in patent: Paragraph 0006; 0016
[2] Organic Letters, 2013, vol. 15, # 11, p. 2742 - 2745
[3] Australian Journal of Chemistry, 1974, vol. 27, p. 2209 - 2228
- 3
[ 69200-16-4 ]- [ 4269-17-4 ]
| Yield | Reaction Conditions | Operation in experiment |
| 36 g |
at 0 - 50℃; for 2.00 h; |
To the crude intermediate 2 (70 g, 0.2525 mol), cone. H0SO4 (1400 mL) was slowly added at 0 °C. The reaction mixture was heated to 50 °C and stirred for 2 h. After 2 h, LCMS monitoring showed complete conversion of starting material. After cooling to room temperature, the mixture was carefully poured into ice water (1000 mL) and stirred for an hour. The precipitated solid was filtered and washed with water (500 mL). The crude product was purified twice by hot acetone crystallization to get 36 g intermediate 3 with 99.54 percent HPLC purity |
Reference：
[1] Organic Letters, 2010, vol. 12, # 24, p. 5648 - 5651
[2] Patent: WO2017/144863, 2017, A1. Location in patent: Page/Page column 26; 27
- 9
[ 19459-33-7 ]- [ 4269-17-4 ]
Reference：
[1] Journal of the Chemical Society, 1952, p. 299,301
[2] Journal of the American Chemical Society, 1935, vol. 57, p. 2443,2446
[3] Yuki Gosei Kagaku Kyokaishi, 1958, vol. 16, p. 304,308[4] Chem.Abstr., 1958, p. 18339
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