Reaktion #77705

Reaktionsgleichung

tricyclohexylphosphine

6-bromo-1,2,3,4-tetrahydrocyclopent[b]indole

potassium (triisopropylsilyl)sulfide

→

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

Ausbeute 73.0%

Lösungsmittel

tetrahydrofuran

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigepre-flushed with argon
2. 2
   Sonstigesubsequently flushed with argon for 5 min before dissolution in toluene (20 mL)
3. 3
   workup.STIRRINGwas stirred for 45 min at room temperature
4. 4
   Temperaturheated at 80° C. (bath temp) for 70 min
5. 5
   Temperaturthen cooled to room temperature over 16 h
6. 6
   SonstigeThe mixture was partitioned between toluene (40 mL) and water (60 mL)
7. 7
   ExtraktionThe separated aqueous layer was extracted with toluene (30 mL)
8. 8
   Waschenthe combined organic extracts were washed with brine (20 mL)
9. 9
   Trocknendried (Na2SO4)
10. 10
    Filtrationfiltered
11. 11
    Einengenconcentrated in vacuo
12. 12
    SonstigeThe residue was purified by column chromatography [SiO2; heptane-ethyl acetate (98:2) to (96:4)]

Vorschrift

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).

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