Tricyclohexylphosphine → 1,2,3,4-Tetrahydro-6-(triisopropylsilyl)thio cyclopent[b]indole

HRID 49427ノート

反応式

HRID 49427 の反応式
C1(P(C2CCCCC2)C2CCCCC2)CCCCC1.Br[C:21]1[CH:22]=[CH:23][C:24]2[C:25]3[CH2:32][CH2:31][CH2:30][C:26]=3[NH:27][C:28]=2[CH:29]=1.[CH:33]([Si:36]([S:43][Si](C(C)C)(C(C)C)C(C)C)([CH:40]([CH3:42])[CH3:41])[CH:37]([CH3:39])[CH3:38])([CH3:35])[CH3:34].[K]>O1CCCC1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.[Pd]>[CH:40]([Si:36]([CH:33]([CH3:35])[CH3:34])([CH:37]([CH3:39])[CH3:38])[S:43][C:21]1[CH:22]=[CH:23][C:24]2[C:25]3[CH2:32][CH2:31][CH2:30][C:26]=3[NH:27][C:28]=2[CH:29]=1)([CH3:42])[CH3:41]

参加物

6

反応物 3

HCID 75806TricyclohexylphosphineHCID 206372566-Bromo-1,2,3,4-tetrahydrocyclopenta[b]indoleHCID 86759386Potassium (triisopropylsilyl)sulfide

生成物 1

HCID 206372531,2,3,4-Tetrahydro-6-(triisopropylsilyl)thio cyclopent[b]indole収率 73%

試薬・触媒・溶媒 2

HCID 72499888Dibenzalacetone palladium触媒HCID 8028Tetrahydrofuran溶媒

実験手順

Palladium dibenzylidene-acetone (0.155 g, 5 mol %) and tricyclohexylphosphine (0.19 g, 20 mol %), were weighed out into a flask pre-flushed with argon, and subsequently flushed with argon for 5 min before dissolution in toluene (20 mL). The deep red mixture was stirred at room temperature for 5 minutes under argon, then 6-bromo-1,2,3,4-tetrahydrocyclopent[b]indole (0.8 g, 3.4 mmol) was added in one portion. After a further 5 min a solution of potassium (triisopropylsilyl)sulfide (Tetrahedron Letts., 1994, 35(20), 3221-3224 and 3225-6)) in tetrahydrofuran (6 mL) was added via syringe over 4 min The mixture was stirred for 45 min at room temperature, heated at 80° C. (bath temp) for 70 min then cooled to room temperature over 16 h. The mixture was partitioned between toluene (40 mL) and water (60 mL). The separated aqueous layer was extracted with toluene (30 mL) and the combined organic extracts were washed with brine (20 mL), dried (Na2SO4), filtered and concentrated in vacuo. The residue was purified by column chromatography [SiO2; heptane-ethyl acetate (98:2) to (96:4)] to yield 1,2,3,4-tetrahydro-6-(triisopropylsilyl)thio cyclopent[b]indole as a pale yellow solid (0.85 g, 73%); NMR (400 MHz, CDCl3) δH 7.76 (1H, br s, NH), 7.43 (1H, d, J 1.5 Hz), 7.27-7.25 (1H, m), 7.18 (1H, dd, J 8.2, 1.5 Hz), 2.85 (2H, obs dt, J 6.9, 1.6 Hz), 2.79 (2H, obs t, J 7.0 Hz), 2.52 (2H, obs quint, J 7.0 Hz), 1.29-1.19 (3H, m), 1.08 (18H, d, J 7.0 Hz); HPLC: [Supelcosil ABZ+; 1.0 ml/min, methanol-10 mM aqueous ammonium acetate solution, (90:10)] 99% (11.1 min).

後処理

  1. custompre-flushed with argon
  2. customsubsequently flushed with argon for 5 min before dissolution in toluene (20 mL)
  3. stirringwas stirred for 45 min at room temperature
  4. temperatureheated at 80° C. (bath temp) for 70 min
  5. temperaturethen cooled to room temperature over 16 h
  6. customThe mixture was partitioned between toluene (40 mL) and water (60 mL)
  7. extractionThe separated aqueous layer was extracted with toluene (30 mL)
  8. washthe combined organic extracts were washed with brine (20 mL)
  9. dry with materialdried (Na2SO4)
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customThe residue was purified by column chromatography [SiO2; heptane-ethyl acetate (98:2) to (96:4)]

出典と根拠

ORDレコード
ord-428887d442ed4346bc4e80e2025780f5
出典データセット
uspto-grants-2004_03
特許番号
US06706750B1

反応ノート

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