1-Butynyltrimethylsilane → tert-Butyl 5-(but-1-yn-1-yl)-7-fluoro-1H-indole-1-carboxylate

HRID 1057136ノート

反応式

HRID 1057136 の反応式
CCCC[N+](CCCC)(CCCC)CCCC.[F-].[C:19]([Si](C)(C)C)#[C:20][CH2:21][CH3:22].[F:27][C:28]1[CH:29]=[C:30](I)[CH:31]=[C:32]2[C:36]=1[N:35]([C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[CH:34]=[CH:33]2>C(OCC)(=O)C.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.[Cu]I>[C:19]([C:30]1[CH:31]=[C:32]2[C:36](=[C:28]([F:27])[CH:29]=1)[N:35]([C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[CH:34]=[CH:33]2)#[C:20][CH2:21][CH3:22]

参加物

7

反応物 3

HCID 439261-Butynyltrimethylsilane2 回HCID 2724141Tetrabutylammonium FluorideHCID 66802356tert-Butyl 7-fluoro-5-iodo-1H-indole-1-carboxylate

生成物 1

HCID 69281207tert-Butyl 5-(but-1-yn-1-yl)-7-fluoro-1H-indole-1-carboxylate収率 91%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418397HCID 178418397、化合物触媒HCID 8857Ethyl Acetate溶媒

実験手順

To a degassed (3× vacuum/nitrogen cycles) solution of TBAF (4.0 mL, 0.5 M THF, 2.00 mmol), but-1-yn-1-yltrimethylsilane (267 mg, 2.11 mmol; Intermediate 39) was added. The solution was stirred at room temperature for a few minutes before transferring into a reaction vessel containing tert-butyl 7-fluoro-5-iodo-1H-indole-1-carboxylate (360 mg, 1.00 mmol), Pd(PPh3)4 (232 mg, 0.20 mmol), and CuI (76 mg, 0.40 mmol). The reaction mixture was stirred at room temperature overnight, diluted with ethyl acetate (100 mL), washed (50 mL water then 50 mL brine), dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to yield the title compound as brown oil (260 mg, 91%). 1H NMR (300 MHz, DMSO-d6): δ 7.85 (d, 1H), 7.58 (d, 1H), 7.21 (dd, 1H), 6.83 (dd, 1H), 2.51 (q, 2H), 1.68 (s, 9H), 1.26 (t, 3H).

後処理

  1. additionwas added
  2. custombefore transferring into a reaction vessel
  3. stirringThe reaction mixture was stirred at room temperature overnight
  4. washwashed (50 mL water
  5. dry with material50 mL brine), dried over Na2SO4
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by silica gel chromatography

出典と根拠

ORDレコード
ord-1c91d1820513409d9a3c5ed68b8407ed
出典データセット
uspto-grants-2016_07
特許番号
US09399646B2

反応ノート

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