三丁基乙烯基锡 → 6-vinyl-1H-indazole

HRID 246035

反应方程式

HRID 246035 反应方程式
Br[C:2]1[CH:10]=[C:9]2[C:5]([CH:6]=[N:7][NH:8]2)=[CH:4][CH:3]=1.[CH2:11]([Sn](CCCC)(CCCC)C=C)[CH2:12]CC>C1(C)C=CC=CC=1.COCCOC.C(OCC)(=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH:11]([C:2]1[CH:10]=[C:9]2[C:5]([CH:6]=[N:7][NH:8]2)=[CH:4][CH:3]=1)=[CH2:12]

参与物

7

反应物 2

HCID 81998三丁基乙烯基锡2 次HCID 178424716-溴吲唑2 次

产物 1

HCID 866779366-vinyl-1H-indazole收率 79.6%

试剂、催化剂与溶剂 4

HCID 178418476HCID 178418476，化合物催化剂2 次HCID 1140甲苯溶剂HCID 8071乙二醇二甲醚溶剂HCID 8857乙酸乙酯溶剂

实验过程

To a suspension of 6-bromo-1H-indazole (600 mg, 3.05 mmol) in toluene (18 ml) and 1,2-dimethoxyethane (6 ml) were added tributyl(vinyl)tin (1.33 ml, 4.57 mmol) and PdCl2(PPh3)2 (214 mg, 0.31 mmol). The reaction was purged with argon then heated at reflux for 3 h. Additional tributyl(vinyl)tin (0.66 ml, 2.28 mmol) and PdCl2(PPh3)2 (107 mg, 0.15 mmol) were added and heating was continued for 1 h. The same reaction was performed on an additional batch of 6-bromo-1H-indazole (200 mg, 1.02 mmol) and the two crude batches were combined. The reactions were diluted with ethyl acetate, washed with water and brine, dried over MgSO4 and concentrated. The residue was purified by silica gel chromatography with 5% to 50% EtOAc/heptane to isolate 350 mg (60%) of 6-vinyl-1H-indazole as a yellow solid. 1H NMR (CDCl3, 300 MHz): δ (ppm) 8.07 (s, 1H), 7.72 (d, J=8.3 Hz, 1H), 7.48 (s, 1H), 7.35 (d, J=8.3 Hz, 1H), 6.85 (dd, J=17.4, 11.0 Hz, 1H), 5.86 (d, J=17.4 Hz, 1H), 5.35 (d, J=11.0 Hz, 1H).

后处理

  1. customThe reaction was purged with argon
  2. temperaturethen heated
  3. temperatureat reflux for 3 h
  4. temperatureheating
  5. customThe same reaction
  6. washwashed with water and brine
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated
  9. customThe residue was purified by silica gel chromatography with 5% to 50% EtOAc/heptane

来源与证据

ORD记录
ord-8738c4ec8dc447b684710ede3a89b834
来源数据集
uspto-grants-2014_02
专利号
US08658646B2

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