1-(3-Nitro-phenyl)vinyltriflate → 6-(1-(3-nitrophenyl)-vinyl)-3-styryl-1-[2-(trimethyl-silanyl)-ethoxymethyl]1H-indazole

HRID 724394ノート

反応式

HRID 724394 の反応式
I[C:2]1[CH:10]=[C:9]2[C:5]([C:6]([CH:19]=[CH:20][C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=3)=[N:7][N:8]2[CH2:11][O:12][CH2:13][CH2:14][Si:15]([CH3:18])([CH3:17])[CH3:16])=[CH:4][CH:3]=1.C([Li])CCC.[N+:32]([C:35]1[CH:36]=[C:37]([C:41](OS(C(F)(F)F)(=O)=O)=[CH2:42])[CH:38]=[CH:39][CH:40]=1)([O-:34])=[O:33]>C1COCC1.[Cl-].[Zn+2].[Cl-].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[N+:32]([C:35]1[CH:36]=[C:37]([C:41]([C:2]2[CH:10]=[C:9]3[C:5]([C:6]([CH:19]=[CH:20][C:21]4[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=4)=[N:7][N:8]3[CH2:11][O:12][CH2:13][CH2:14][Si:15]([CH3:18])([CH3:17])[CH3:16])=[CH:4][CH:3]=2)=[CH2:42])[CH:38]=[CH:39][CH:40]=1)([O-:34])=[O:33]

参加物

7

反応物 3

HCID 218774861-(3-Nitro-phenyl)vinyltriflateHCID 693701476-iodo-3-styryl-1-[2-(trimethyl-silanyl)ethoxymethyl]-1H-indazoleHCID 178418339Butyllithium

生成物 1

HCID 693714336-(1-(3-nitrophenyl)-vinyl)-3-styryl-1-[2-(trimethyl-silanyl)-ethoxymethyl]1H-indazole収率 52%

試薬・触媒・溶媒 3

HCID 3007855Zincchloride触媒HCID 178418397HCID 178418397、化合物触媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
23 °C

実験手順

To a solution of 6-iodo-3-styryl-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1H-indazole, prepared in Example 14, step (i), (330 mg, 0.693 mmol) in THF (3.0 mL) at −78° C. was added n-butyllithium (0.56 mL, 1.5 M, 1.2 equiv). After 20 min, this solution was then added to anhydrous zinc chloride (170 mg) and the mixture was warmed to 23° C. and stirred for 15 min. To this mixture was added 1-(3-nitro-phenyl)vinyltriflate (146 μL, 1.05 equiv) and Pd(PPh3)4 (40 mg, 0.05 equiv). This mixture was stirred for 30 min, was partitioned between ethyl acetate and saturated sodium bicarbonate and the organic layer was separated. The organic material was dried over sodium sulfate, decanted and concentrated under reduced pressure. Purification by silica gel chromatography (1:9 ethyl acetate-hexane) then a second column (1% ethyl acetate/benzene) gave 6-(1-(3-nitrophenyl)-vinyl)-3-styryl-1-[2-(trimethyl-silanyl)-ethoxymethyl]-1H-indazole as an oil (180 mg, 52%): FTIR (thin film) 2951, 1616, 1530, 1477, 1448, 1348, 1305, 1248, 1217, 1077, 961, 913, 859 cm−1; 1H NMR (300 MHz, CDCl3) δ 8.26 (t, 1H, J=1.9 Hz), 8.21 (m, 1H), 8.00 (d, 1H, J=8.5 Hz), 7.69 (dt, 1H, J=1.4, 7.8), 7.62–7.28 (m, 9H), 7.19 (dd, 1H, J=1.4, 8.4 Hz), 5.72 (s, 3H), 5.69 (s, 1H), 3.60 (t, 2H, J=8.2 Hz), 0.89 (t, 2H, J=8.2 Hz), −0.05 (s, 9H); 13C NMR (75 MHz, CDCl3) δ 149.9, 149.6, 144.7, 144.5, 142.8, 140.7, 138.6, 135.6, 133.1, 130.7, 130.2, 129.4, 128.0, 124.4, 124.2, 124.1, 123.8, 122.6, 121.2, 118.9, 111.0, 79.2, 68.0, 19.2, 0.0; HRMS (FAB) [M+Na]/z Calc'd 520.2031. found 520.2046.

後処理

  1. stirringThis mixture was stirred for 30 min
  2. customwas partitioned between ethyl acetate and saturated sodium bicarbonate
  3. customthe organic layer was separated
  4. dry with materialThe organic material was dried over sodium sulfate
  5. customdecanted
  6. concentrationconcentrated under reduced pressure
  7. customPurification by silica gel chromatography (1:9 ethyl acetate-hexane)

出典と根拠

ORDレコード
ord-04f4dbb34a9b4cb6aa163f5fd9c3ea15
出典データセット
uspto-grants-2006_11
特許番号
US07141587B2

反応ノート

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