Dichloromethane → (S)-ethyl 2-tert-butoxy-2-(7-(4-chlorophenyl)-2-(2-(1,3-dimethyl-1H-pyrrolo[2,3-b]pyridin-5-yl)pyridine-4-yl)-5-methylbenzo[d]thiazol-6-yl)acetate

HRID 879393Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 879393
Br[C:2]1[N:7]=[C:6]2[N:8]([CH3:12])[CH:9]=[C:10]([CH3:11])[C:5]2=[CH:4][CH:3]=1.B1(B2OC(C)(C)C(C)(C)O2)OC(C)(C)C(C)(C)O1.ClCCl.C([O-])(=O)C.[K+].[C:39]([O:43][C@H:44]([C:50]1[C:65]([CH3:66])=[CH:64][C:53]2[N:54]=[C:55]([C:57]3[CH:62]=[CH:61][N:60]=[C:59](Cl)[CH:58]=3)[S:56][C:52]=2[C:51]=1[C:67]1[CH:72]=[CH:71][C:70]([Cl:73])=[CH:69][CH:68]=1)[C:45]([O:47][CH2:48][CH3:49])=[O:46])([CH3:42])([CH3:41])[CH3:40].C([O-])([O-])=O.[K+].[K+]>O1CCOCC1.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.O>[C:39]([O:43][C@@H:44]([C:50]1[C:65]([CH3:66])=[CH:64][C:53]2[N:54]=[C:55]([C:57]3[CH:62]=[CH:61][N:60]=[C:59]([C:3]4[CH:4]=[C:5]5[C:10]([CH3:11])=[CH:9][N:8]([CH3:12])[C:6]5=[N:7][CH:2]=4)[CH:58]=3)[S:56][C:52]=2[C:51]=1[C:67]1[CH:68]=[CH:69][C:70]([Cl:73])=[CH:71][CH:72]=1)[C:45]([O:47][CH2:48][CH3:49])=[O:46])([CH3:40])([CH3:41])[CH3:42]

Komponenten

10

Edukt 6

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 867001976-bromo-1,3-dimethyl-1H-pyrrolo[2,3-b]pyridineHCID 86700200(R)-ethyl 2-tert-butoxy-2-(7-(4-chlorophenyl)-2-(2-chloropyridin-4-yl)-5-methylbenzo[d]thiazol-6-yl)acetate

Produkt 1

HCID 86700199(S)-ethyl 2-tert-butoxy-2-(7-(4-chlorophenyl)-2-(2-(1,3-dimethyl-1H-pyrrolo[2,3-b]pyridin-5-yl)pyridine-4-yl)-5-methylbenzo[d]thiazol-6-yl)acetate

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

To a solution of 6-bromo-1,3-dimethyl-1H-pyrrolo[2,3-b]pyridine (15 mg, 0.067 mmol) in dioxane (1 mL) was added bis(pinacolato)diboron (20 mg, 0.080 mmol), [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex with dichloromethane (5.5 mg, 0.0067 mmol), potassium acetate (20 mg, 0.201 mmol). The mixture was degassed and heated at 100° C. for 2 h. The mixture was cooled, and then added (R)-ethyl 2-tert-butoxy-2-(7-(4-chlorophenyl)-2-(2-chloropyridin-4-yl)-5-methylbenzo[d]thiazol-6-yl)acetate (24 mg, 0.045 mmol), tetrakis(triphenylphosphine)palladium(0) (5 mg, 0.0045 mmol), K2CO3 (31 mg, 0.227 mmol) and water (0.3 mL, degassed). The reaction mixture was heated at 110° C. for 1 h, cooled and partitioned between ethyl acetate and brine. The organic layer was separated, dried over Na2SO4 and concentrated to give crude which was purified by chromatographic column to afford the desired product. LCMS-ESI+: calc'd for C36H35ClN4O3S: 639.3 (M+H+); Found: 639.3 (M+H+).

Aufarbeitung

  1. customThe mixture was degassed
  2. temperatureThe mixture was cooled
  3. temperatureThe reaction mixture was heated at 110° C. for 1 h
  4. temperaturecooled
  5. custompartitioned between ethyl acetate and brine
  6. customThe organic layer was separated
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated
  9. customto give crude which
  10. customwas purified by chromatographic column

Quellen und Nachweise

ORD-Eintrag
ord-b57112b55df74f6ab825ab49386abab2
Quelldatensatz
uspto-grants-2015_03
Patentnummer
US08987250B2

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